Compounds for Reducing Background Color in Color Change Compositions

ABSTRACT

Aspects of the invention include color change compositions having a color former and color developer composition that transitions from a first color state to a second color state upon application of an applied stimulus and an amount of a copolymer sufficient to eliminate background color of the color former and color developer composition during transition from the first color state to the second color state. Methods for preparing and devices employing the color change compositions of the invention are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

Pursuant to 35 U.S.C. §119 (e), this application claims priority to thefiling dates of U.S. Provisional Patent Application Ser. No. 61/790,612filed Mar. 15, 2013; the disclosure of which application is hereinincorporated by reference.

INTRODUCTION

Many products, including consumer and industrial products, are moreeffectively used by an end user when they include a feature thatindicates that the product has undergone exposure to a particularstimulus or by a degree of use. One example of an indicator featurewhich can indicate that a product has undergone exposure to stimuli is acolor indicator. Color indicators can either indicate a change incondition or a degree of use through a change from colored to uncolored,from uncolored to colored or through a change from one color to adifferent color.

Consumer products may be able to be more effective and deliver morebenefits to end users by incorporating a suitable color indicator sothat the end user is unambiguously aware of any exposure to stimuli orintends on applying the stimuli to achieve a desired result. It isdesirable, where the indicator is a color change, for the colorindicator to have a distinct, or sharp, color change and a rapidresponse time to aid the user in identifying that the product hasundergone exposure to a particular stimulus.

Thus, there remains a need for a composition that shows rapid, distinctand acute color changes for use in a variety of different industrial andcommercial products where color change offers unambiguous determinationif stimuli has been applied.

SUMMARY

Aspects of the invention include color change compositions having acolor former and color developer composition that transitions from afirst color state to a second color state upon application of an appliedstimulus and an amount of a copolymer sufficient to eliminate backgroundcolor of the color former and color developer composition duringtransition from the first color state to the second color state. Methodsfor preparing and devices employing the color change compositions of theinvention are also described.

In embodiments of the invention, color change compositions include anamount of a copolymer sufficient to eliminate background color duringtransition from a first color state to a second color state which has aformula (I):

where n is an integer from 10 to 1000; m is an integer from 10 to 1000;and R is an alkyl, substituted alkyl, alkenyl, substituted alkenyl,alkynyl, substituted alkynyl, acyl, substituted acyl, acyloxy,substituted acyloxy, alkoxycarbonyl, substituted alkoxycarbonyl,carboxyl or substituted carboxyl.

In certain embodiments, n is an integer from 10 to 1000; m is an integerfrom 10 to 1000 and R is an acyloxy group or substituted acyloxy group.Where R is an acyloxy group or substituted acyloxy group, in certaininstances, the copolymer is a polymer having formula (II):

where n is an integer from 10 to 1000; m is an integer from 10 to 1000;and R_(a) is hydrogen, alkyl or substituted alkyl. In some embodiments,R_(a) is a C1-C12 alkyl or a C1-C12 substituted alkyl. Where R_(a) is aC1-C12 alkyl, in certain instances R_(a) is a C1-C6 alkyl such as methylor ethyl. In some embodiments, R_(a) is methyl. In other embodiments,R_(a) is ethyl. In certain embodiments, the copolymer of formula (II) isethyl vinyl acetate.

In certain embodiments, n is an integer from 10 to 1000; m is an integerfrom 10 to 1000 and R is an alkoxycarbonyl or substitutedalkoxycarbonyl. Where R is an alkoxycarbonyl or substitutedalkoxycarbonyl, in certain instances, the copolymer is a polymer havingformula (III):

where n is an integer from 10 to 1000; m is an integer from 10 to 1000;and R_(b) is hydrogen, alkyl or substituted alkyl. In some embodimentsR_(b) is a C1-C12 alkyl or a C1-C12 substituted alkyl. Where R_(b) is aC1-C12 alkyl, in certain instances R_(b) is a C1-C6 alkyl such as methylor ethyl. In some embodiments, R_(b) is methyl. In other embodiments,R_(b) is ethyl. In other embodiments, R_(b) is propyl. In yet otherembodiments, R_(b) is butyl. In certain embodiments, the copolymer offormula (III) is selected from ethylene methyl acrylate, ethylene ethylacrylate and ethylene butyl acrylate.

Color change compositions of interest according to certain embodimentsinclude an amount of copolymer which ranges from 0.01% to 15% by weight,such as 0.5% to 12% by weight and including 1% to 10% by weight wherethe amount of copolymer is sufficient to eliminate background color ofthe color change composition during transition from a first color stateto a second color state.

In embodiments of the invention, the color change composition includes acolor former and color developer composition. The color former and colordeveloper composition may be single component systems where a singlecolor former and single color developer are employed in the subjectcolor change compositions. Alternatively, the color former and colordeveloper composition may be a multi-component system where a pluralityof color formers are paired with one or more color developers, asdesired. In certain embodiments the color former and color developercomposition includes one or more color formers and a single colordeveloper. The color former and color developer system may be reversibleor irreversible and in certain embodiments, exhibit hysteresis. Further,color former and color developer compositions of interest may bemicroencapsulated systems where one or both of the color former andcolor developer are microencapsulated.

Color change compositions may further include additional pigments,coloring agents, dyes and the like, in addition to various excipients,such as anti-oxidants, fillers, preservatives, plasticizers, softeningor hardening agents, adhesives, tackifying agents, viscosity modifiers,resins, buffers, among other excipients.

Aspects of the invention also include methods for preparing the subjectcolor change compositions. In embodiments of the invention, methods forpreparing color change compositions of interest include combining acolor former and color developer composition with an amount of acopolymer to produce a color change composition which changes from afirst color state to a second color state upon application of an appliedstimulus. In some embodiments, the method includes combining the colorformer and color developer composition with the copolymer as a colorformer-color developer pseudo master batch composition. Where the colorformer and color developer is combined with the copolymer as a pseudomaster batch composition, methods may further include preparing thecolor former-color developer pseudo master batch composition, whichincludes combining an aqueous slurry of the color former and colordeveloper with a plastic emulsifier (e.g., anionic, cationic ornon-ionic) and plastic resin to produce a mixture and flash drying themixture to produce a color former-color developer pseudo master batchcomposition. The pseudo master batch may be in the form of a powder,flakes or in granular form.

Devices employing the subject color change compositions are alsodescribed. In some embodiments, devices include the color changecomposition applied to at least one surface of a substrate, in certaininstances in the shape of a pattern, word or in a machine readableformat. For example, the color change compositions may be employed as anink printed onto a substrate such as paper, plastic, hard surfaces, softsurfaces, stiff or rigid surfaces, compliant surfaces, printed surfaces,printable surfaces, transparent surfaces, semi-transparent surfaces,opaque surfaces, non-transparent surfaces, skin, finger nails, moldedsurfaces, flexo-graphic printing surfaces, foam surfaces, expandedplastic surfaces, insulating surfaces, conducting surfaces andconducting ink surfaces.

Selected Definitions of Chemical Terminology

The following chemical terminology has the following meanings unlessotherwise indicated. Any undefined terms have their art recognizedmeanings.

Many general references providing commonly known chemical syntheticschemes and conditions useful for synthesizing the disclosed compoundsare available (see, e.g., Smith and March, March's Advanced OrganicChemistry: Reactions, Mechanisms, and Structure, Fifth Edition,Wiley-Interscience, 2001; or Vogel, A Textbook of Practical OrganicChemistry, Including Qualitative Organic Analysis, Fourth Edition, NewYork: Longman, 1978).

Chemical compounds as described herein can be purified by any of themeans known in the art, including chromatographic means, such as highperformance liquid chromatography (HPLC), preparative thin layerchromatography, flash column chromatography and ion exchangechromatography. Any suitable stationary phase can be used, includingnormal and reversed phases as well as ionic resins. See, e.g.,Introduction to Modern Liquid Chromatography, 2nd Edition, ed. L. R.Snyder and J. J. Kirkland, John Wiley and Sons, 1979; and Thin LayerChromatography, ed E. Stahl, Springer-Verlag, New York, 1969.

Depending on the particular embodiment, the compounds described hereinmay contain one or more chiral centers and/or double bonds andtherefore, can exist as stereoisomers, such as double-bond isomers(i.e., geometric isomers), enantiomers or diastereomers. Accordingly,all possible enantiomers and stereoisomers of the compounds includingthe stereoisomerically pure form (e.g., geometrically pure,enantiomerically pure or diastereomerically pure) and enantiomeric andstereoisomeric mixtures are included in the description of the compoundsherein. Enantiomeric and stereoisomeric mixtures can be resolved intotheir component enantiomers or stereoisomers using separation techniquesor chiral synthesis techniques well known to the skilled artisan. Thecompounds can also exist in several tautomeric forms including the enolform, the keto form and mixtures thereof. Accordingly, the chemicalstructures depicted herein encompass all possible tautomeric forms ofthe illustrated compounds. The compounds described also includeisotopically labeled compounds where one or more atoms have an atomicmass different from the atomic mass conventionally found in nature.Examples of isotopes that can be incorporated into the compoundsdisclosed herein include, but are not limited to, ²H, ³H, ¹¹C, ¹³C, ¹⁴C,¹⁵N, ¹⁸O, ¹⁷O, etc. In general, all physical forms are equivalent forthe uses contemplated herein and are intended to be within the scope ofthe present disclosure.

As used herein, the term “alkyl” by itself or as part of anothersubstituent refers to a saturated branched or straight-chain monovalenthydrocarbon radical derived by the removal of one hydrogen atom from asingle carbon atom of a parent alkane. Typical alkyl groups include, butare not limited to, methyl; ethyl, propyls such as propan-1-yl orpropan-2-yl; and butyls such as butan-1-yl, butan-2-yl,2-methyl-propan-1-yl or 2-methyl-propan-2-yl. In some embodiments, analkyl group comprises from 1 to 20 carbon atoms. In other embodiments,an alkyl group comprises from 1 to 10 carbon atoms. In still otherembodiments, an alkyl group comprises from 1 to 6 carbon atoms, such asfrom 1 to 4 carbon atoms.

The term “substituted” as used herein refers to a group in which one ormore hydrogen atoms are independently replaced with the same ordifferent substituent(s). Typical substituents include, but are notlimited to, alkylenedioxy (such as methylenedioxy), -M, —R⁶⁰, —O⁻, ═O,—OR⁶⁰, —SR⁶⁰, —S⁻, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CF₃, —CN, —OCN, —SCN, —NO,—NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂OH, —S(O)₂R⁶⁰, —OS(O)₂O⁻, —OS(O)₂R⁶⁰,—P(O)(O⁻)₂, —P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰, —C(S)R⁶⁰,—C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻, —C(S)OR⁶⁰, —NR⁶²C(O)NR⁶⁰R⁶¹,—NR⁶²C(S)NR⁶⁰R⁶¹, —NR⁶²C(NR⁶³)NR⁶⁰R⁶¹ and —C(NR⁶²)NR⁶⁰R⁶¹ where M ishalogen; R⁶⁰, R⁶¹, R⁶² and R⁶³ are independently hydrogen, alkyl,substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substitutedcycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, aryl,substituted aryl, heteroaryl or substituted heteroaryl, or optionallyR⁶⁰ and R⁶¹ together with the nitrogen atom to which they are bondedform a cycloheteroalkyl or substituted cycloheteroalkyl ring; and R⁶⁴and R⁶⁵ are independently hydrogen, alkyl, substituted alkyl, aryl,cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substitutedcycloheteroalkyl, aryl, substituted aryl, heteroaryl or substitutedheteroaryl, or optionally R⁶⁴ and R⁶⁵ together with the nitrogen atom towhich they are bonded form a cycloheteroalkyl or substitutedcycloheteroalkyl ring. In certain embodiments, substituents include -M,—R⁶⁰, ═O, —OR⁶⁰, —SR⁶⁰, —S⁻, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CF₃, —CN, —OCN, —SCN,—NO, —NO₂, ═N₂, —N₃, —S(O)₂R⁶⁰, —OS(O)₂O⁻, —OS(O)₂R⁶⁰, —P(O)(O⁻)₂,—P(O)(OR⁶⁰)(O⁻), —OP(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰, —C(S)R⁶⁰, —C(O)OR⁶⁰,—C(O)NR⁶⁰R⁶¹, —C(O)O—, —NR⁶²C(O)NR⁶⁰R⁶¹. In certain embodiments,substituents include -M, —R⁶⁰, ═O, —OR⁶⁰, —SR⁶⁰, —NR⁶⁰R⁶¹, —CF₃, —CN,—NO₂, —S(O)₂R⁶⁰, —P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰,—C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻. In certain embodiments, substituentsinclude -M, —R⁶⁰, ═O, —OR⁶⁰, —SR⁶⁰, —NR⁶⁰R⁶¹, —CF₃, —CN, —NO₂,—S(O)₂R⁶⁰, —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰, —C(O)OR⁶⁰, —C(O)O⁻, where R⁶⁰,R⁶¹ and R⁶² are as defined above. For example, a substituted group maybear a methylenedioxy substituent or one, two, or three substituentsselected from a halogen atom, a (1-4C)alkyl group and a (1-4C)alkoxygroup.

“Alkanyl” by itself or as part of another substituent refers to asaturated branched, straight-chain or cyclic alkyl radical derived bythe removal of one hydrogen atom from a single carbon atom of an alkane.Typical alkanyl groups include, but are not limited to, methanyl;ethanyl; propanyls such as propan-1-yl, propan-2-yl (isopropyl),cyclopropan-1-yl, etc.; butanyls such as butan-1-yl, butan-2-yl(sec-butyl), 2-methyl-propan-1-yl (isobutyl), 2-methyl-propan-2-yl(t-butyl), cyclobutan-1-yl, etc.; and the like.

“Alkylene” refers to a branched or unbranched saturated hydrocarbonchain, usually having from 1 to 40 carbon atoms, more usually 1 to 10carbon atoms and even more usually 1 to 6 carbon atoms. This term isexemplified by groups such as methylene (—CH₂—), ethylene (—CH₂CH₂—),the propylene isomers (e.g., —CH₂CH₂CH₂— and —CH(CH₃)CH₂—) and the like.

“Alkenyl” by itself or as part of another substituent refers to anunsaturated branched, straight-chain or cyclic alkyl radical having atleast one carbon-carbon double bond derived by the removal of onehydrogen atom from a single carbon atom of an alkene. The group may bein either the cis or trans conformation about the double bond(s).Typical alkenyl groups include, but are not limited to, ethenyl;propenyls such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl), prop-2-en-2-yl, cycloprop-1-en-1-yl; cycloprop-2-en-1-yl;butenyls such as but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl,but-2-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl,buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl,cyclobuta-1,3-dien-1-yl, etc.; and the like.

“Alkynyl” by itself or as part of another substituent refers to anunsaturated branched, straight-chain or cyclic alkyl radical having atleast one carbon-carbon triple bond derived by the removal of onehydrogen atom from a single carbon atom of an alkyne. Typical alkynylgroups include, but are not limited to, ethynyl; propynyls such asprop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyls such as but-1-yn-1-yl,but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like.

“Acyl” by itself or as part of another substituent refers to a radical—C(O)R³⁰, where R³⁰ is hydrogen, alkyl, cycloalkyl, cycloheteroalkyl,aryl, arylalkyl, heteroalkyl, heteroaryl, heteroarylalkyl as definedherein and substituted versions thereof. Representative examplesinclude, but are not limited to formyl, acetyl, cyclohexylcarbonyl,cyclohexylmethylcarbonyl, benzoyl, benzylcarbonyl, piperonyl, succinyl,and malonyl, and the like.

The term “aminoacyl” refers to the group —C(O)NR²¹R²², wherein R²¹ andR²² independently are selected from the group consisting of hydrogen,alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl,substituted alkynyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, cycloalkenyl, substituted cycloalkenyl, heteroaryl,substituted heteroaryl, heterocyclic, and substituted heterocyclic andwhere R²¹ and R²² are optionally joined together with the nitrogen boundthereto to form a heterocyclic or substituted heterocyclic group, andwherein alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl,substituted alkynyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl,substituted cycloalkenyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, heterocyclic, and substituted heterocyclic areas defined herein.

“Alkoxy” by itself or as part of another substituent refers to a radical—OR³¹ where R³¹ represents an alkyl or cycloalkyl group as definedherein. Representative examples include, but are not limited to,methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy and the like.

“Alkoxycarbonyl” by itself or as part of another substituent refers to aradical —C(O)OR³¹ where R³¹ represents an alkyl or cycloalkyl group asdefined herein. Representative examples include, but are not limited to,methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl,cyclohexyloxycarbonyl and the like.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon radical derived by the removal of onehydrogen atom from a single carbon atom of an aromatic ring system.Typical aryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexalene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene and the like. In certain embodiments, an aryl groupcomprises from 6 to 20 carbon atoms. In certain embodiments, an arylgroup comprises from 6 to 12 carbon atoms. Examples of an aryl group arephenyl and naphthyl.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Typical arylalkyl groups include, but are not limited to,benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl and/orarylalkynyl is used. In certain embodiments, an arylalkyl group is(C₇-C₃₀) arylalkyl, e.g., the alkanyl, alkenyl or alkynyl moiety of thearylalkyl group is (C₁-C₁₀) and the aryl moiety is (C₆-C₂₀). In certainembodiments, an arylalkyl group is (C₇-C₂₀) arylalkyl, e.g., thealkanyl, alkenyl or alkynyl moiety of the arylalkyl group is (C₁-C₈) andthe aryl moiety is (C₆-C₁₂).

“Arylaryl” by itself or as part of another substituent, refers to amonovalent hydrocarbon group derived by the removal of one hydrogen atomfrom a single carbon atom of a ring system in which two or moreidentical or non-identical aromatic ring systems are joined directlytogether by a single bond, where the number of such direct ringjunctions is one less than the number of aromatic ring systems involved.Typical arylaryl groups include, but are not limited to, biphenyl,triphenyl, phenyl-napthyl, binaphthyl, biphenyl-napthyl, and the like.When the number of carbon atoms in an arylaryl group are specified, thenumbers refer to the carbon atoms comprising each aromatic ring. Forexample, (C₅-C₁₄) arylaryl is an arylaryl group in which each aromaticring comprises from 5 to 14 carbons, e.g., biphenyl, triphenyl,binaphthyl, phenylnapthyl, etc. In certain embodiments, each aromaticring system of an arylaryl group is independently a (C₅-C₁₄) aromatic.In certain embodiments, each aromatic ring system of an arylaryl groupis independently a (C₅-C₁₀) aromatic. In certain embodiments, eacharomatic ring system is identical, e.g., biphenyl, triphenyl,binaphthyl, trinaphthyl, etc.

“Carboxyl,” “carboxy” or “carboxylate” refers to —CO₂H or salts thereof.“Carboxyl ester” or “carboxy ester” or the terms “carboxyalkyl” or“carboxylalkyl” refers to the groups —C(O)O-alkyl, —C(O)O-substitutedalkyl, —C(O)O-alkenyl, —C(O)O-substituted alkenyl, —C(O)O-alkynyl,—C(O)O-substituted alkynyl, —C(O)O-aryl, —C(O)O-substituted aryl,—C(O)O-cycloalkyl, —C(O)O-substituted cycloalkyl, —C(O)O-cycloalkenyl,—C(O)O— substituted cycloalkenyl, —C(O)O-heteroaryl, —C(O)O-substitutedheteroaryl, —C(O)O-heterocyclic, and —C(O)O-substituted heterocyclic,wherein alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl,substituted alkynyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl,substituted cycloalkenyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, heterocyclic, and substituted heterocyclic areas defined herein.

“(Carboxyl ester)oxy” or “carbonate” refers to the groups —O—C(O)O—alkyl, —O—C(O)O-substituted alkyl, —O—C(O)O-alkenyl,—O—C(O)O-substituted alkenyl, —O—C(O)O-alkynyl, —O—C(O)O-substitutedalkynyl, —O—C(O)O-aryl, —O—C(O)O-substituted aryl, —O—C(O)O-cycloalkyl,—O—C(O)O-substituted cycloalkyl, —O—C(O)O-cycloalkenyl, —O—C(O)O—substituted cycloalkenyl, —O—C(O)O-heteroaryl, —O—C(O)O-substitutedheteroaryl, —O—C(O)O-heterocyclic, and —O—C(O)O-substitutedheterocyclic, wherein alkyl, substituted alkyl, alkenyl, substitutedalkenyl, alkynyl, substituted alkynyl, cycloalkyl, substitutedcycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substitutedaryl, heteroaryl, substituted heteroaryl, heterocyclic, and substitutedheterocyclic are as defined herein.

“Cycloalkyl” by itself or as part of another substituent refers to asaturated or unsaturated cyclic alkyl radical. Where a specific level ofsaturation is intended, the nomenclature “cycloalkanyl” or“cycloalkenyl” is used. Typical cycloalkyl groups include, but are notlimited to, groups derived from cyclopropane, cyclobutane, cyclopentane,cyclohexane and the like. In certain embodiments, the cycloalkyl groupis (C₃-C₁₀) cycloalkyl. In certain embodiments, the cycloalkyl group is(C₃-C₇) cycloalkyl.

“Cycloheteroalkyl” or “heterocyclyl” by itself or as part of anothersubstituent, refers to a saturated or unsaturated cyclic alkyl radicalin which one or more carbon atoms (and any associated hydrogen atoms)are independently replaced with the same or different heteroatom.Typical heteroatoms to replace the carbon atom(s) include, but are notlimited to, N, P, O, S, Si, etc. Where a specific level of saturation isintended, the nomenclature “cycloheteroalkanyl” or “cycloheteroalkenyl”is used. Typical cycloheteroalkyl groups include, but are not limitedto, groups derived from epoxides, azirines, thiiranes, imidazolidine,morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine,quinuclidine and the like.

“Heteroalkyl, Heteroalkanyl, Heteroalkenyl and Heteroalkynyl” bythemselves or as part of another substituent refer to alkyl, alkanyl,alkenyl and alkynyl groups, respectively, in which one or more of thecarbon atoms (and any associated hydrogen atoms) are independentlyreplaced with the same or different heteroatomic groups. Typicalheteroatomic groups which can be included in these groups include, butare not limited to, —O—, —S—, —S—S—, —O—S—, —NR³⁷R³⁸—, .═N—N═, —N═N—,—N═N—NR³⁹R⁴⁰, —PR⁴¹—, —P(O)₂—, —POR⁴²—, —O—P(O)₂—, —S—O—, —S—(O)—,—SO₂—, —SnR⁴³R⁴⁴— and the like, where R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³and R⁴⁴ are independently hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl,substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl,heteroalkyl, substituted heteroalkyl, heteroaryl, substitutedheteroaryl, heteroarylalkyl or substituted heteroarylalkyl.

“Heteroarylalkyl” by itself or as part of another substituent, refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylalkenyl and/orheterorylalkynyl is used. In certain embodiments, the heteroarylalkylgroup is a 6-30 membered heteroarylalkyl, e.g., the alkanyl, alkenyl oralkynyl moiety of the heteroarylalkyl is 1-10 membered and theheteroaryl moiety is a 5-20-membered heteroaryl. In certain embodiments,the heteroarylalkyl group is 6-20 membered heteroarylalkyl, e.g., thealkanyl, alkenyl or alkynyl moiety of the heteroarylalkyl is 1-8membered and the heteroaryl moiety is a 5-12-membered heteroaryl.

DETAILED DESCRIPTION

Aspects of the invention include color change compositions having acolor former and color developer composition that transitions from afirst color state to a second color state upon application of an appliedstimulus and an amount of a copolymer sufficient to eliminate backgroundcolor of the color former and color developer composition duringtransition from the first color state to the second color state. Methodsfor preparing and devices employing the color change compositions of theinvention are also described.

Before the present invention is described in greater detail, it is to beunderstood that this invention is not limited to particular embodimentsdescribed, as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present invention will be limited only by the appendedclaims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the invention, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present invention is not entitled to antedate suchpublication by virtue of prior invention. Further, the dates ofpublication provided may be different from the actual publication dateswhich may need to be independently confirmed.

It is noted that, as used herein and in the appended claims, thesingular forms “a”, “an”, and “the” include plural referents unless thecontext clearly dictates otherwise. It is further noted that the claimsmay be drafted to exclude any optional element. As such, this statementis intended to serve as antecedent basis for use of such exclusiveterminology as “solely,” “only” and the like in connection with therecitation of claim elements, or use of a “negative” limitation.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentinvention. Any recited method can be carried out in the order of eventsrecited or in any other order which is logically possible.

As reviewed above, the present invention provides color changecompositions having a color former and color developer composition and acopolymer, as well as methods for preparing and devices employing thecolor change compositions of the invention. In further describingembodiments of the invention, color change compositions are firstreviewed in greater detail. Next, methods for preparing the subjectcompositions are described. Devices employing the color changecompositions are also described.

Color Change Compositions

As summarized above, the subject invention provides color changecompositions having a color former and color developer composition thattransitions from a first color state to a second color state uponapplication of an applied stimulus and an amount of a copolymersufficient to eliminate background color of the color former and colordeveloper composition during transition from the first color state tothe second color state. By “eliminate background color” is meant thatthe copolymer is present in an amount where the initial color of thecolor change composition is reduced or altogether removed after thecolor change composition has transitioned to the second color. In otherwords, when the copolymer is present in the subject compositions, thecolor change composition retains 5% or less of the initial color in thecomposition as determined by visual inspection (e.g., by the human eyeor a computer employing an optical detector device), such as 3% or lessof the initial color, such as 1% or less of the initial color, such as0.5% or less of the initial color, such as 0.1% or less the initialcolor and including retaining 0.01% or less of the initial color in thecomposition. In certain embodiments, the amount of copolymer present inthe subject composition is sufficient completely remove all of theresidual background color such that the color change composition retainsnone of the initial color of the composition as determined by visualinspection.

For example, in some embodiments where the first color state of thecolor change composition is red and the second color state is green, anamount of the copolymer is present in compositions of interest that issufficient to reduce or altogether remove any residual red color in thecomposition after the color change composition has transitioned to thegreen color state. In these embodiments, the color change compositionretains 5% or less of the red color after transitioning to the greencolor state, such as 3% or less of the red color, such as 1% or less ofthe red color, such as 0.5% or less of the red color, such as 0.1% orless the red color and including retaining 0.01% or less of the redcolor in the composition after the color change composition hastransitioned to the green color state.

In embodiments of the invention, compositions of interest change colorupon application of an applied stimulus. Stimuli sufficient for inducinga color change transition may be a variety of different types ofphysicochemical stimuli, depending on device employing the subjectcompositions, as described in greater detail below. As such, the appliedstimulus (i.e., color change triggering processes) may include but isnot limited to light, mechanical perturbation, changes in temperature,change in pH, chemical exposure, biochemical exposure, ionization, stateof hydration, state of solvation, hydrogen bonding, protonation. Thus,color change compositions may be photochromic, mechanochromic,thermochromic, solvatochromic, hydrochromic or halochromic compositions,among other color change compositions.

Copolymer Compounds

As reviewed above, color change compositions of the present inventioninclude an amount of a copolymer sufficient to eliminate backgroundcolor of the color former and color developer composition duringtransition from the first color state to the second color state. Inembodiments of the invention, copolymers of interest include the classof polymeric compounds described by the formula:

where n is an integer from 10 to 1000, m is an integer from 10 to 1000and R is alkyl, substituted alkyl, alkenyl, substituted alkenyl,alkynyl, substituted alkynyl, acyl, substituted acyl, acyloxy,substituted acyloxy, alkoxycarbonyl, substituted alkoxycarbonyl,carboxyl or substituted carboxyl.

In certain embodiments, R is an acyloxy group or substituted acyloxygroup. The term “acyloxy” is used in its conventional sense to refer tosubstituents having the general structure —C(O)OR¹, where R¹ ishydrogen, alkyl, cycloalkyl, cycloheteroalkyl, aryl, arylalkyl,heteroalkyl, heteroaryl, heteroarylalkyl.

Where R is an acyloxy group or a substituted acyloxy group, in certaininstances, the copolymer is a polymer having formula (II):

where n is an integer from 10 to 1000; m is an integer from 10 to 1000;and R_(a) is hydrogen, alkyl or substituted alkyl. In some embodiments,R_(a) is a C1-C12 alkyl or a C1-C12 substituted alkyl. Where R_(a) is aC1-C12 alkyl, in certain instances R_(a) is a C1-C6 alkyl such as methylor ethyl. In some embodiments, R_(a) is methyl. In other embodiments,R_(a) is ethyl. In certain embodiments, the copolymer of formula (II) isethyl vinyl acetate.

In certain embodiments, R is an alkoxycarbonyl group or substitutedalkoxycarbonyl group. Where R is an alkoxycarbonyl group or substitutedalkoxycarbonyl group, in certain instances, the copolymer is a polymerhaving formula (III):

where n is an integer from 10 to 1000; m is an integer from 10 to 1000;and R_(b) is hydrogen, alkyl or substituted alkyl. In some embodimentsR_(b) is a C1-C12 alkyl or a C1-C12 substituted alkyl. Where R_(b) is aC1-C12 alkyl, in certain instances R_(b) is a C1-C6 alkyl such as methylor ethyl. In some embodiments, R_(b) is methyl. In other embodiments,R_(b) is ethyl. In other embodiments, R_(b) is propyl. In yet otherembodiments, R_(b) is butyl. In certain embodiments, the copolymer offormula (III) is selected from ethylene methyl acrylate, ethylene ethylacrylate and ethylene butyl acrylate.

The size of the copolymer may vary, where n ranges from 10 to 1000, suchas 25 to 900, such as 50 to 800, such as 75 to 750, such as 100 to 500,such as 150 to 400 and including where n ranges from 200 to 300.Likewise, the size of the copolymer may vary where m ranges from 10 to1000, such as 25 to 900, such as 50 to 800, such as 75 to 750, such as100 to 500, such as 150 to 400 and including where n ranges from 200 to300. As such, the molecular weight of the subject copolymers may be 1kDa or greater, such as 10 kDa or greater, such as 15 kDa or greater,such as 25 kDa or greater, such as 40 kDa or greater, such as 50 kDa orgreater, such as 60 kDa or greater, such as 75 kDa or greater andincluding 100 kDa or greater.

The ratio of n and m in copolymers of interest may vary depending on thedesired properties of the copolymer in the subject color changecompositions. For example, the ratio of n and m may range between 1:1and 1:10, such as between 1:1 and 1:9, such as between 1:1 and 1:8, suchas between 1:1 and 1:7, such as between 1:1 and 1:6, such as between 1:1and 1:5, such as between 1:1 and 1:4, such as between 1:1 and 1:3 andincluding between 1:1 and 1:2. In other embodiments, the ratio of n andm may range between 1:1 and 10:1, such as between 1:1 and 9:1, such asbetween 1:1 and 8:1, such as between 1:1 and 7:1, such as between 1:1and 6:1, such as between 1:1 and 5:1, such as between 1:1 and 4:1, suchas between 1:1 and 3:1 and including between 1:1 and 2:1.

The amount of copolymer in color change compositions of the inventionmay vary depending on the particular color former and color developercompositions, method of color change, the initial and final colors inthe color transition from the first color state to second color state,ranging from 0.01% to 15% w/w, such as 0.05% to 14% w/w, such as 0.1% to13% w/w, such as 0.5% to 12% w/w, such as 0.75% to 11% w/w, such as 1%to 10% w/w, such as 1.5% to 8.5% w/w, such as 2.5% to 7.5% w/w andincluding 3% to 6% w/w. Any convenient amount from 0.01% to 15% w/w maybe employed in the subject compositions so long as the amount issufficient to eliminate background color by reducing or altogetherremoving any residual color from the initial color state after thecomposition has transitioned to the second color state as determined byvisual inspection.

The mass ratio of the copolymer to color former and color developercomposition may vary, in some embodiments ranging between 1:1 and 1:1.5;1:1.5 and 1:2; 1:2 and 1:2.5; 1:2.5 and 1:3; 1:3 and 1:3.5; 1:3.5 and1:4; 1:4 and 1:4.5; 1:4.5 and 1:5, or a range thereof. For instance, themass ratio of copolymer to color former and color developer compositionmay range between 1:1 and 1:5, such as 1:1 and 1:4.5, such as 1:1 and1:4, such as 1:1 and 1:3.5, such as 1:1 and 1:3, such as 1:1 and 1:2.5,such as 1:1 and 1:2, including 1:1 and 1:1.5. In other embodiments, themass ratio of color former and color developer composition to copolymermay range between 1:1 and 1:2; 1:1 and 1:3; 1:1 and 1:4; or 1:1 and 1:5.For instance, the mass ratio of color former and color developercomposition to copolymer may range between 1:1 and 1:5, such as 1:1 and1:4.5, such as 1:1 and 1:4, such as 1:1 and 1:3.5, such as 1:1 and 1:3,such as 1:1 and 1:2.5, such as 1:1 and 1:2, including 1:1 and 1:1.5.

Color Former and Color Developer Compositions

As reviewed above, color change compositions of the present inventioninclude a composition having a color former and a color developer thattransitions from a first color state to a second color state uponapplication of an applied stimulus. In embodiments of the invention, thetransition from a first color state to a second color state uponapplication of an applied stimulus may be one or more of: 1) atransition from a colorless state to a colored state; 2) a transitionfrom a colored state to a colorless state; 3) a transition from atransparent state to a translucent or opaque state; 4) a transition froma translucent or opaque state to a transparent state; 5) a transitionfrom a glossy state to a matte state; 6) a transition from a matte stateto a glossy state; 7) a transition from a first color to a second,different color. In certain embodiments, the color change compositiontransitions from a colorless state to a colored state under the appliedstimulus. In other embodiments, the color change composition transitionsfrom a colored state to a colorless state under the applied stimulus. Inyet other embodiments, the color change composition transitions from afirst color to a second, different color under the applied stimulus.

As described in greater detail below, the stimulus for inducing thesubject color change transitions may vary depending on the type of colorchange composition desired. For example the physicochemical stimuli(i.e., color change triggering processes) may include but is not limitedto light, mechanical perturbation, changes in temperature, change in pH,chemical exposure, biochemical exposure, ionization, state of hydration,state of solvation, hydrogen bonding, protonation. Thus, color changecompositions may be photochromic, mechanochromic, thermochromic,solvatochromic hydrochromic and halochromic compositions, among othercolor change compositions. In certain embodiments, the subject colorchange compositions are thermochromic compositions where the appliedstimulus sufficient for transition from a first color state to a secondcolor state is a change in temperature (e.g., heat or cooling). In otherembodiments, the subject color change compositions are halochromiccompositions where the applied stimulus is a change in the pH.

The color transitions may be irreversible or reversible. In someembodiments, the color transitions are irreversible, i.e., the colorchange composition transitions from a first color state to a secondcolor state and remains in the second color state for the remaininglifetime of the color change composition.

Alternatively, the color state may be reversible, i.e., the color changecomposition is capable of transition back from the second color state tothe first color state after initial chromic transition. Depending on thecolor change composition desired, reversible color change compositionsof the interest may be capable of transitioning from a first color stateto a second color state or from the second color state back to the firstcolor state any suitable number of times. For example, the color changecomposition may be capable of 5 color transitions or more, such as 10color transitions or more, such as 25 color transitions or more, such as50 color transitions or more, such as 100 color transitions or more,such as 250 color transitions or more, such as 500 color transitions ormore and including 1000 color transitions or more. Either reversible orirreversible color formers can be employed depending on the desiredembodiment of interest. For instance, reversible color formers can beemployed where it is desirable to have a multi-use effect or reuse thecolor change effect. In these embodiments, it may be desirable toutilize a reversible thermochromic color former which is capable of 5color transitions or more, such as 25 color transitions or more andincluding 1000 color transitions or more. In other instances, it may bedesirable to record a single permanent color change. In theseembodiments, an irreversible color former which changes color only asingle time may be employed. For example, disposable indicatorcompositions may employ a color former having an irreversible chromictransition.

In embodiments of the invention, the term “color former” is used hereinto refer to the component of the color change composition which exhibitsthe visible transition from the first color state to the second colorstate. Depending on the type of physicochemical stimuli, the type ofcolor former compound may vary. For example, the color former may be aphotochromic compound, a mechanochromic compound, a thermochromiccompound, a solvatochromic compound, a hydrochromic compound or ahalochromic compound, among other color change compositions. As such,the color former may exhibit a visible transition from a first colorstate to a second color state in response to light, mechanicalperturbation, changes in temperature, change in pH, chemical exposure,biochemical exposure, ionization, a change in state of hydration, achange in state of solvation, hydrogen bonding or protonation. Forexample, photochromic, mechanochromic, thermochromic, solvatochromic,hydrochromic and halochromic color transitions may include those asdescribed in U.S. patent application Ser. No. 13/572,526, the disclosureof which is herein incorporated by reference

In certain embodiments, the color former is a thermochromic compound.The term “thermochromic” is used in its conventional sense to refer to acompound which changes color state in response to a change intemperature (i.e., heating or cooling). Depending on the desired colorchange composition, temperature transitions of color formers of interestmay vary widely, and may be at about −25° C. or higher, such as at about−15° C. or higher, such as at about −5° C. or higher, such as at about0° C. or higher, such as at about 5° C. or higher, such as at about 10°C. or higher, such as at about 20° C. or higher, such as at about 25° C.or higher, such as at about 35° C. or higher, such as at about 50° C. orhigher, such as at about 75° C. or higher, such as at about 90° C. orhigher, such as at about 100° C. or higher, such as at about 110° C. orhigher and including at about 125° C. or higher. In certain embodiments,the temperature transitions occur in a range of temperatures, such as arange between −25° C. to 125° C., such as a range between −15° C. to115° C., such as a range between −5° C. to 105° C., such as a rangebetween 0° C. to 100° C., such as a range between 10° C. to 90° C., suchas a range between 20° C. to 80° C., such as a range between 30° C. to70° C. and including a range between 40° C. to 60° C.

Example thermochromic dyes of interest as color formers in the subjectcolor change compositions may include but are not limited tobis(2-amino-4-oxo-6-methylpyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium) tetrachlorocuprate(II) andbis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorodicuprate(II),benzo- and naphthopyrans (Chromenes), poly(xylylviologen dibromide,di-beta-naphthospiropyran, Ferrocene-modified bis(spiropyridopyran),isomers of1-isopropylidene-2-[1-(2-methyl-5-phenyl-3-thienyl)ethylidene]-succinicanhydride and the photoproduct7,7adihydro-4,7,7,7a-tetramethyl-2-phenylbenzo[b]thiophene-5,6-dicarboxylic anhydride, micro-encapsulated dyes,precise melting point compositions, infra-red dyes, spirobenzopyrans,spironnapthooxazines, spirothopyran and related compounds, leuco quinonedyes, natural leuco quinone, traditional leuco quinone, syntheticquinones, thiazine leuco dyes, acylated leuco thiazine dyes, nonacylatedleuco thiazine dyes, oxazine leuco dyes, acylated oxazine dyes,nonacylated oxazine leuco dyes, catalytic dyes, combinations with dyedevelopers, arylmethane phthalides, diarylmethane phthalides,monoarylmethane phthalides, monoheterocyclic substituted phthalides,3-hetercyclic substituted phthalides, diarylmethylazaphthalides,bishetercyclic substituted phthalides, 3,3-bisheterocyclic substitutedphthalides, 3-heterocyclic substituted azaphthalides,3,3-bisheterocyclic substituted azaphthalides, alkenyl substitutedphthalides, 3-ethylenyl phthalides, 3,3-bisethylenyl phthalides,3-butadienyl phthalides, bridged phthalides, spirofluorene phthalides,spirobensanthracene phthalides, bisphthalides, di and triarylmethanes,diphenylmethanes, carbinol bases, pressure sensitive recrcordingchemistries, photosensitive recording chemistries, fluoran compounds,reaction of keto acids and phenols, reactions of keto acids with4-alkoxydiphenylamines, reactions of keto acids sith3-alkoxdiphenylamines, reactions of 2′-aminofluorans with aralkylhalides, reaction of 3′-chlorofluorans with amines, thermally sensitiverecording mediums, tetrazolium salts, tetrazolium salts from formazans,tetrazolium salts from tetrazoles, and the like. Additionalthermochromic compounds of interest may include, but are not limited to:light-induced metastable state in a thermochromic copper (II) complex(see e.g., Chem. Commun., 2002, (15), 1578-1579) which under goes acolor change from red to purple for a thermochromic complex,[Cu(dieten)2](BF4)2 (dieten=N,N-diethylethylenediamine);bis(2-amino-4-oxo-6-methyl-pyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium) tetrachlorocuprate(II) andbis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorodicuprate(II),benzo- and naphthopyrans (chromenes), poly(xylylviologen dibromide,di-beta-naphthospiropyran, Ferrocene-modified bis(spiropyridopyran),isomers of1-isopropylidene-2-[1-(2-methyl-5-phenyl-3-thienyl)ethylidene]-succinicanhydride and the photoproduct7,7adihydro-4,7,7,7a-tetramethyl-2-phenylbenzo[b]thiophene-5,6-dicarboxylic anhydride, and the like.

In certain embodiments, the color former is a leuco dye, includingcompounds exhibiting colored to colorless transitions, colorless tocolored transitions or a transition from a first color to a second,different color. Leuco dyes of interest may include, but are not limitedto vinylphenylmethane-leucocyanides and derivatives, fluoran dyes andderivatives, thermochromic pigments, micro and nano-pigments, molybdenumcompounds, doped or undoped vanadium dioxide, indolinospirochromenes,melting waxes, encapsulated dyes, liquid crystalline materials,cholesteric liquid crystalline materials, spiropyrans, polybithiophenes,bipyridine materials, microencapsulated, mercury chloride dyes, tincomplexes and combination thermochromic/photochromic materials. The typeof color former compound may vary depending on the desired color changecomposition, associated costs, amount added, type of color changedesired, level of color contrast, levels or color hue change,reversibility or irreversibility, stability, among other factors.

In some embodiments, color former compounds include diacetylenicpolydiacetylene polymers, including but not limited to2,3-dihydroxypropyl-10,12-dodecadiynoate (2,3-DHP-10,12-C12);2,3-DHP-10,12-C13; 2,3-DHP-10,12-C14; 2,3-DHP-10,12-C15;2,3-DHP-10,12-C16; 2,3-DHP-10,12-C17; 2,3-DHP-10,12-C18;2,3-DHP-10,12-C19; 2,3-DHP-10,12-C20; 2,3-DHP-10,12-C21;2,3-DHP-10,12-C22; 2,3-DHP-10,12-C23; 2,3-DHP-10,12-C24;2,3-DHP-10,12-C25; 2,3-DHP-10,12-C26; 2,3-DHP-10,12-C27;2,3-DHP-10,12-C28; 2,3-DHP-10,12-C29 and 2,3-DHP-10,12-C30 among otherdiacetylenic compounds.

In certain embodiments, diacetylenic color former compounds of theinvention include those described in U.S. patent application Ser. No.12/643,887, the disclosure of which is herein incorporated by reference.

The color change exhibited by the color former may be any desiredchromic transition. For example, colored to colorless transitions mayinclude, but are not limited to: yellow to colorless, orange tocolorless, red to colorless, pink to colorless, magenta to colorless,purple to colorless, blue to colorless, turquoise to colorless, green tocolorless, brown to colorless and black to colorless among other coloredto colorless transitions. Colorless to colored transitions may include,but are not limited to: colorless to yellow, colorless to orange,colorless to red, colorless to pink, colorless to magenta, colorless topurple, colorless to blue, colorless to turquoise, colorless to green,colorless to brown and colorless to black, among other colorless tocolored transitions. In some embodiments, the chromic transition is achange from a first color to a second, different color. For example,color to color transitions may include, but are not limited to: orangeto yellow, orange to pink, orange to very light green, orange to peach;red to yellow, red to orange, red to pink, red to light green, red topeach; magenta to yellow, magenta to orange, magenta to pink, magenta tolight green, magenta to light blue; purple to red, purple to pink,purple to blue; blue to pink; blue to light green, dark blue to lightyellow, dark blue to light green, dark blue to light blue; turquoise tolight green, turquoise to light blue, turquoise to light yellow,turquoise to light peach, turquoise to light pink; green to yellow, darkgreen to orange, dark green to light green, dark green to light pink;brown and black to a variety of assorted colors, among other color tocolor transitions.

In certain embodiments, the chromic transition is a change from red togreen. In other embodiments, the chromic transition is a change fromgreen to red. Where the chromic transition is a change from red to greenor a change from green to red, in certain embodiments, two differentleuco dyes are mixed together to achieve the chromic transition. Inthese embodiments, one leuco dye may be a colored to colorless dye and asecond leuco dye may be a colorless to colored dye where the first leucodye and the second leuco dye undergo chromic transition in response tothe same applied stimulus (e.g., heat, cooling). In combination, the twodifferent leuco dyes are capable of forming chromic transitionspreviously unattainable by chromic change compositions. In addition, theresulting combination of color to colorless and colorless to color indifferent combinations permits the possibility of heretofore notrealized color overlap such that stationary colors do not interfere withthe initial or final color.

The amount of color former in compositions of the invention may varydepending on the particular color former and color developercompositions, stimulus of color change, type of chromic transition,where in some embodiments the amount ranges from 1% to 30% w/w, such as2% to 28% w/w, such as 3% to 25% w/w, such as 4% to 23% w/w, such as 5%to 22% w/w, such as 7% to 20% w/w, such as 8% to 18% w/w, such as 9% to17% w/w and including 10% to 15% w/w.

Color former and color developer compositions of interest furtherinclude a color developer. In embodiments of the invention, the term“color developer” is used to refer to the component of the color changecomposition which facilitates chromic transitions in the color formercompound. In certain instances, the color developer compound may undergoa phase transition upon exposure to the applied stimulus, where thephase transition is sufficient to initiate the chromic transition of thecolor former. For example, the phase transition may be a transition fromsolid to liquid, a transition from liquid to solid, a transition fromliquid to gas, a transition from gas to liquid, a transition from solidto gas or a transition from gas to liquid. In certain embodiments, thephase transition is a transition from liquid to solid or a transitionfrom solid to liquid.

Compositions according to certain embodiments include single componentcolor developers. By single component color developer is meant that thecolor developer consists of only one compound. As such, where the colordeveloper is a single compound, no additional compounds are present inthe color former and color developer composition other than the one ormore color former compounds (which provides the chromic transition) andthe color developer compound. In these embodiments, the color developerfunctions as both the solvent and color developer components of thecolor former and color developer composition. In some instances, singlecomponent developers assist in controlling the chromic transition by itsability to anneal or un-anneal depending on the particular phasetransition to create or to abandon a charge transfer complexes throughphase dissociation and association processes.

Color developer compounds of interest include, but are not limited toglycerol monostearate derivatives, low acidic phase associatingcompounds, mild protonating phase associating compounds, and the like.In some embodiments, color developer compounds may be esterified,hydroxyl containing compounds. For example, glycerol monostearatederivatives may include, but are not limited to: 2,3-dihydroxypropyl C5;2,3-dihydroxypropyl C7; 2,3-dihydroxypropyl C8; 2,3-dihydroxypropyl C9;2,3-dihydroxypropyl C10; 2,3-dihydroxypropyl C11; 2,3-dihydroxypropylC12; 2,3-dihydroxypropyl C13; 2,3-dihydroxypropyl C14;2,3-dihydroxypropyl C15; 2,3-dihydroxypropyl C16; 2,3-dihydroxypropylC17; 2,3-dihydroxypropyl C18; 2,3-dihydroxypropyl C19;2,3-dihydroxypropyl C20; 2,3-dihydroxypropyl C21; 2,3-dihydroxypropylC22; 2,3-dihydroxypropyl C23; 2,3-dihydroxypropyl C24;2,3-dihydroxypropyl C25; 2,3-dihydroxypropyl C26; 2,3-dihydroxypropylC27; 2,3-dihydroxypropyl C28; 2,3-dihydroxypropyl C29;2,3-dihydroxypropyl C30; 3,4-dihydroxybutyl C5; 3,4-dihydroxybutyl C6;3,4-dihydroxybutyl C7; 3,4-dihydroxybutyl C8; 3,4-dihydroxybutyl C9;3,4-dihydroxybutyl C11; 3,4-dihydroxybutyl C12; 3,4-dihydroxybutyl C13;3,4-dihydroxybutyl C14; 3,4-dihydroxybutyl C15; 3,4-dihydroxybutyl C16;3,4-dihydroxybutyl C17; 3,4-dihydroxybutyl C18; 3,4-dihydroxybutyl C19;3,4-dihydroxybutyl C20; 3,4-dihydroxybutyl C21; 3,4-dihydroxybutyl C22;3,4-dihydroxybutyl C23; 3,4-dihydroxybutyl C24; 3,4-dihydroxybutyl C25;3,4-dihydroxybutyl C26; 3,4-dihydroxybutyl C27; 3,4-dihydroxybutyl C28;3,4-dihydroxybutyl C29 and 3,4-dihydroxybutyl C30, among other glycerolmonostearate derivatives.

In some embodiments, color developer compounds include diacetylenicpolydiacetylene polymers, including but not limited to2,3-dihydroxypropyl-10,12-dodecadiynoate (2,3-DHP-10,12-C12);2,3-DHP-10,12-C13; 2,3-DHP-10,12-C14; 2,3-DHP-10,12-C15;2,3-DHP-10,12-C16; 2,3-DHP-10,12-C17; 2,3-DHP-10,12-C18;2,3-DHP-10,12-C19; 2,3-DHP-10,12-C20; 2,3-DHP-10,12-C21;2,3-DHP-10,12-C22; 2,3-DHP-10,12-C23; 2,3-DHP-10,12-C24;2,3-DHP-10,12-C25; 2,3-DHP-10,12-C26; 2,3-DHP-10,12-C27;2,3-DHP-10,12-C28; 2,3-DHP-10,12-C29 and 2,3-DHP-10,12-C30 among otherdiacetylenic compounds.

In certain embodiments, the color former and the color developer areboth diacetylenic compounds, such as for example polydiacetylenepolymers. Where both the color former and color developer are bothdiacetylenic compounds, in some instances the color former and colordeveloper are the same diacetylenic compound. In other embodiments, thecolor former and the color developer are different diacetyleniccompounds. In certain instances, the color former compound and the colordeveloper compound are co-topo-polymeric diacetylenic compounds composedof two different co-crystallized diacetylenic monomers. Exampleco-topo-polymeric diacetylenic compositions of interest include thosedescribed in U.S. Pat. No. 8,187,892, the disclosure of which is hereinincorporated by reference in its entirety.

In other embodiments, color developer compounds may include estercontaining compounds having a hydroxylated esterifying group. Exampleester containing color developer compounds include, but are not limitedto n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate,n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonylcaprylate, n-undecyl caprylate, n-tridecyl caprylate, n-pentadecylcaprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate,n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, n-heptyllaurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate,n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonylmyristate, n-undecyl myristate, n-tridecyl myristate, n-pentadecylmyristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate,n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate,n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecylstearate, n-nonyl icosanoate, n-undecyl icosanoate, n-tridecylicosanoate, n-pentadecyl icosanoate, n-nonyl behenate, n-undecylbehenate, n-tridecyl behenate, and n-pentadecyl behenate among otherester containing compounds.

In yet other embodiments, color developer compounds may betert-butylphenol, nonylphenol, dodecyl phenol, styrenated phenols,2,2-methylene-bis-(4-methyl-6-tert-butylphenol), .alpha.-naphthol,.beta.-naphthol, hydroquinemonomethyl-ether, guaiacol, eugenol,p-chlorophenol, p-bromophenol, o-chlorophenol, o-bromophenol, o-phenylphenol, p-phenyl phenol, p-(p-chlorophenyl)-phenol,o-(o-chlorophenyl)-phenol, p-methyl hydroxy benzoate, p-ethyl hydroxybenzoate, p-octyl hydroxy benzoate, p-butyl hydroxy benzoate, p-octylhydroxy benzoate, p-dodecyl hydroxy benzoate, 3-iso-propyl catechol,p-tert-butyl catechol, 4,4-methylene diphenol,4,4-chio-bis-(6-tert-butyl-3-methyphenol),1,1-bis-(4-hydroxyphenol)-cyclohexane,4,4-butylidene-bis-(6-tert-butyl-3-methylphenol, bisphenol A, bisphenolS, 1,2-dioxynaphtaleine, 2,3-dioxynaphthalein, chlorocatechol, bromocatechol, 2,4-dihydroxybenzophenon, pheno phtalein, o-cresol phthalein,methyl protocatechinate, ethyl protocatechinate, propylprotocatechinate, octyl protocatechinate, dodecyl protocatechinate,2,4,6-trioxymethyl benzene, 2,3,4-trioxyethyl benzene, methyl gallicate,ethyl gallicate, propyl gallicate, butyl gallicate, hexyl gallicate,octyl gallicate, dodecyl gallicate, cetyl gallicate, stearyl gallicate,2,3,5-trioxynaphthalein, tannin acid and phenol resins.

In yet other embodiments, the color developer may be a polymer. In someinstances, the polymer is a polyacrylic acid or a polyacrylic acidester. A variety of small to large molecular weight polyacrylic acids(PAA) can be utilized. The molecular weight, degree of polymerization,mobility, proton donating characteristics, adhesive bindingcharacteristics, melting point characteristics, phase transition,density, molecular weight cutoff, degree of chemical modification andassociated binding resin of a polymeric color developer compound can beadjusted as desired to precisely fit the specifically paired colorformer, stimulus of color change as well as type of chromic transitionand temperature of color change.

Acrylic acid monomers, oligomers, low molecular weight polymers, mediummolecular weight polymers, and high molecular weight polymers may be ofinterest. Depending on the properties of the developer desired, theacrylic acid monomers, oligomers or polymers may range be 0.05 kDa orgreater, such as 0.1 kDa or greater, such as 1 kDa or greater, such as 5kDa or greater, such as 10 kDa or greater, such as 25 kDa or greater,such as 50 kDa or greater, such as 100 kDa or greater, such as 500 kDaor greater, such as 1000 kDa or greater, such as 5000 kDa or greater,such as 10,000 kDa or greater, such as 25,000 kDa or greater andincluding 50,000 kDa or greeter.

In yet other embodiments, the color developer is a natural food gradecompound. For example, the natural food-grade color developer may becamauba wax. Carnauba wax contains mainly esters of fatty acids(80-85%), fatty alcohols (10-16%), acids (3-6%) and hydrocarbons (1-3%).Specific for camauba wax is the content of esterified fatty diols (about20%), hydroxylated fatty acids (about 6%) and cinnamic acid (about 10%).Cinnamic acid, an antioxidant, may be hydroxylated or methoxylated.

In certain embodiments, color developer compounds of the inventioninclude glycerol monostearate derivatives, polydiacetylenic compoundsand polymeric compositions as described in U.S. patent application Ser.No. 12/643,887, the disclosure of which is herein incorporated byreference.

The amount of color developer in compositions of the invention may varydepending on the particular color former and color developercompositions, type of color developer (e.g., glycerol monostearate,carnauba wax, etc.) stimulus of color change, type of chromictransition, where in some embodiments the amount ranges from 0.1% to 99%w/w, such as 0.5% to 95% w/w, such as 1% to 90% w/w, such as 5% to 85%w/w, such as 10% to 80% w/w, such as 15% to 75% w/w, such as 20% to 70%w/w, such as 25% to 65% w/w and including 30% to 60% w/w.

The mass ratio of the color former to color developer in the subjectcompositions may vary, in some embodiments ranging between 1:1 and1:100, such as between 1:1 and 1:95, such as between 1:1 and 1:90, suchas between 1:1 and 1:85, such as between 1:1 and 1:80, such as between1:1 and 1:75, such as between 1:1 and 1:50, such as between 1:1 and1:25, such as between 1:1 and 1:10 and including between 1:1 and 1:5 ora range thereof. For instance, the mass ratio of copolymer to colorformer and color developer composition may range between 1:1 and 1:25,such as between 1:1 and 1:20, such as between 1:1 and 1:15, such asbetween 1:1 and 1:10 and including between 1:1 and 1:5.

In some embodiments, one or more of the components of the subjectcompositions may be microencapsulated. The term “microencapsulated” isused in its conventional sense to refer to surrounding or enveloping oneor more compounds within a capsule of another compound, yieldingmicrocapsules having diameters that range from less than one micron toseveral hundred microns in size. For example, microcapsules provided bythe invention may have diameters ranging from 1 μm to 1000 μm, such as 5μm to 900 μm, such as 10 μm to 800 μm, such as 25 μm to 750 μm andincluding 50 μm to 500 μm. Microcapsules may include a homogeneousmixture of the one or more compounds within the microcapsule or may havea plurality of distinct droplets of each compound.

In embodiments of the invention, one or more of the color former andcolor developer can be microencapsulated. For example, the color formeralone may be encapsulated or the color developer alone may beencapsulated. Alternatively, both the color former and color developermay be both encapsulated within the same microcapsule. Even still, eachof the color former and color developer may be individuallymicroencapsulated. Additives (e.g., antioxidants, binding agents,solvents, etc.) to the subject compositions, as described in greaterdetail below, may also be microencapsulated, as desired.

Microencapsulation may be achieved by any suitable technique dependingon the application of interest. Compositions may be microencapsulatedwith the intention that the core material be confined within capsulewalls for a predetermined period of time. Alternatively, core materialsmay be encapsulated so that the core material will be released eithergradually through the capsule walls through controlled release ordiffusion, or when external conditions (e.g., heat, acid, light, etc.)trigger the capsule walls to rupture, melt, or dissolve.

Microencapsulation can be achieved by chemical processes and mechanicalor physical processes including, but not limited to bulk fluidprocesses, phase separation processes, chemical processes, mechanicalshear processes and milling processes. Compositions discussed herein canbe microencapsulated using coacervation, interfacial polymerization,polymer-polymer incompatibility, phase separation processes,oil-in-water encapsulation, centrifugal processes, high-shear processes,mechanical drying processes, fluid bed coating, Wusrster processes,centrifugal extrusion, ultrasonication/coating, rotational suspension,double wall micro-encapsulation, chemical silanization processes,liposomal encapsulation, in-line printing/layering processes,heat/chilling cycling, embedding, in-situ polymerization,urea-formaldehyde systems, melamine formaldehyde systems, impregnation,particle coating, and a variety of other micro-particleformation/microencapsulation processes or the like.

Complex coacervation may be employed to microencapsulate any of thecompositions described herein. In the subject coacervation processgelatin having a high iso-electric point and gum arabic containing manycarboxyl groups are added to a core-containing suspension at relativelylow pH above 35° C. The gelatin and gum Arabic react to formmicrodroplets of polymer coacervate which separate. The wall can besubsequently hardened by several means such as by the addition offormaldehyde or glutaraldehyde. In the final steps, the suspension ofmicrocapsules is cooled and the pH raised after which the suspension isfiltered leaving the microcapsules on the filter media.

Additional Components

Depending on the particular color former and color developercompositions, stimulus of color change, type of chromic transition,compositions of the invention may further include one or more additives.Additives may be added to modify one or more characteristics of thechromic transition (e.g., rate of transition, temperature to initiatecolor change) or may be added to modify a physical property of thecomposition (e.g., viscosity, tackiness, etc.).

In some embodiments, the color former and color developer compositionfurther includes a solvent. Of interest are solvents that do not blockthe chromic transitions facilitated by the color developer oralternatively provides for the raising or lowering of the temperaturetransition of a particular color change composition. Non-interferingsolvents of interest may include mineral oils, low temperature waxes,chloroform, methylethyl ketone, alkyl alcohols, branched or non-branchedhydrocarbons such as for example n-Decane; n-Decene; n-Dodecane;n-Dodecene; n-Tetradecane; n-Tetradecene; n-Hexadecane; n-Hexadecene;n-Octadecane; n-Octadecene; n-Eicosane; n-Eicosene and parrifin blend.

In certain embodiments, the solvent is a long-chain hydrocarbon.Depending on the color former and color developer, long-chainhydrocarbon can include, but are not limited to hydrocarbons havingchain lengths of C10, C11, C12, C13, C14, C15, C16, C18, C19, C20, C21,C22, C23, C24, C25, C26, C27, C28, C29, C30 and longer synthetic and/ornaturally derived hydrocarbon chain lengths.

In certain embodiments, the solvent is a microcrystalline wax, paraffinbase or long chain alcohol for dispersion (or as a carrier) of the colorformer compound, such as for example those described in U.S. patentapplication Ser. No. 12/643,887, the disclosure of which is hereinincorporated by reference in its entirety.

When present, the amount of solvent in compositions of the invention mayvary depending on the particular color former and color developercompositions, stimulus of color change, type of chromic transition,where in some embodiments the amount ranges from 0.0001% to 99% w/w,such as 0.001% to 95% w/w, such as 0.01% to 90% w/w, such as 0.1% to 85%w/w, such as 0.5% to 80% w/w, such as 1% to 75% w/w, such as 5% to 70%w/w, such as 10% to 65% w/w and including 1% to 25% w/w.

In some embodiments, the solvent is a component which promotestemperature hysteresis. Solvents which provide temperature hysteresisfor compositions of the invention may include, but are not limited tostearyl 2-methylbenzoate, cetyl 4-tert-butylbenzoate, behenyl4-cyclohexylbenzoate, myristyl 4-phenylbenzoate, lauryl 4-octylbenzoate,hexyl 3,5-dimethylbenzoate, stearyl 3-ethylbenzoate, butyl4-benzylbenzoate, octyl 3-methyl-5-chlorobenzoate, decyl4-isopropylbenzoate, stearyl 4-benzoylbenzoate, stearyl 1-naphthoate,cetyl phenylacetate, stearyl phenylacetate, phenyl 4-tert-butylbenzoate,4-chlorobenzyl 2-methyl benzoate, stearyl 4-chlorobenzoate, myristyl3-bromobenzoate, stearyl 2-chloro-4-bromobenzoate, decyl3,4-dichlorobenzoate, octyl 2,4-dibromobenzoate, cetyl 3-nitrobenzoate,cyclohexyl 4-aminobenzoate, cyclohexylmethyl 4-amino benzoate, cetyl4-diethyklaminobenzoate, stearyl 4-aminobenzoate, decyl4-methoxybenzoate, cetyl 4-methoxybenzoate, stearyl 4-methoxybenzoate,octyl 4-butoxybenzoate, cetyl 4-butoxybenzoate, 4-methoxybenzylbenzoate, cetyl p-chlorophenylacetate, stearyl p-chlorophenylacetate,decyl 3-benzoylpropionate, cyclohexyl 2-benzoylpropionate, myristylbenzoate, cetyl benzoate, stearyl benzoate, 4-chlorobenzyl benzoate,benzyl cinnamate, cyclohexylmethyl cinnamate, benzyl caproate,4-chlorobenzyl caprate, 4-methoxybenzyl myristate, 4-methoxy benzylstearate, benzyl palmitate, 4-nitrobenzyl stearate, neopentyl caprylate,neopentyl laurate, neopentyl stearate, neopentyl behenate, cyclohexyllaurate, cyclohexyl myristate, cyclohexyl palmitate, cyclohexylmethylstearate, 2-cyclohexyl ethyl stearate, stearyl cyclohexylpropionate,3-phenylpropyl stearate, 4-methoxybenzyl caproate, 4-methoxybenzylcaprate, 2-chlorobenzyl myristate, 4-isopropylbenzyl stearate, phenyl11-bromolaurate, 4-chlorophenyl 11-bromolaurate, didecyl adipate,dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyladipate, dibenzyl sebacate, distearyl tere-phthalate, dineopentyl4,4′-diphenyldicarboxylate, dibenzyl azodicaroboxylate, trilaurin,trimyristin, tristearin, dimyristin and distearin.

When present, the amount of solvent for promoting temperature hysteresisin compositions of the invention may vary depending on the particularcolor former and color developer compositions, stimulus of color change,type of chromic transition, where in some embodiments the amount rangesfrom 0.0001% to 99% w/w, such as 0.001% to 95% w/w, such as 0.01% to 90%w/w, such as 0.1% to 85% w/w, such as 0.5% to 80% w/w, such as 1% to 75%w/w, such as 5% to 70% w/w, such as 10% to 65% w/w and including 1% to25% w/w.

Where the color former and color developer composition is athermochromic system which undergoes a color change in response to achange in temperature (e.g., heat, cooling), additives that modifychromic transition temperatures may also be included in the subjectcolor change compositions. By “modifying” chromic transitiontemperatures is meant that the temperature threshold for chromictransition is increased or decreased by adding one or more of thetemperature modifying additives. Additives for modifying chromictransition temperatures in thermochromic color change compositions ofinterest may include, but are not limited to oils including organic,natural, inorganic, and synthetic oils such as corn oil, variousvegetables oils, nut oils, root oils, herbal oils, paraffin oils,greases, animal fats, natural extract oils, flavor based oils, aromaticbased oils, industrial oils, among other types of oil.

When present, the amount of additive for modifying chromic transitiontemperature in compositions of the invention may vary depending on theparticular color former and color developer compositions, stimulus ofcolor change, type of chromic transition, where in some embodiments theamount ranges from 0.0001% to 99% w/w, such as 0.001% to 95% w/w, suchas 0.01% to 90% w/w, such as 0.1% to 85% w/w, such as 0.5% to 80% w/w,such as 1% to 75% w/w, such as 5% to 70% w/w, such as 10% to 65% w/w andincluding 1% to 25% w/w.

In some embodiments, color change compositions may also include one ormore antioxidants or preservatives. Antioxidants of interest mayinclude, but are not limited to water soluble antioxidants, such asascorbic acid, cysteine hydrochloride, sodium bisulfate, sodiummetabisulfite, sodium sulfite among other water soluble antioxidants;oil-soluble antioxidants, such as ascorbyl palmitate, butylatedhydroxyanisole (BHA), butylated hydroxytoluene (BHT), lecithin, propylgallate, alpha-tocopherol, among other oil-soluble antioxidants; as wellas metal chelating agents, such as citric acid, ethylenediaminetetraacetic acid (EDTA), sorbitol, tartaric acid, phosphoric acid, amongother chelating agents.

The amount of antioxidant or preservatives in compositions of theinvention may vary depending on the particular color former and colordeveloper compositions, stimulus of color change, type of chromictransition, where in some embodiments the amount ranges from 0.0001% to99% w/w, such as 0.001% to 95% w/w, such as 0.01% to 90% w/w, such as0.1% to 85% w/w, such as 0.5% to 80% w/w, such as 1% to 75% w/w, such as5% to 70% w/w, such as 10% to 65% w/w and including 1% to 25% w/w.

Color change compositions of the invention may further include one ormore adhesives, such as for example where the color change compositionmay be employed as an tape, such as a specialty tape, repositionabletape, packing tape, permanent label, peelable-resealable tape, amongother types of tapes.

Where compositions include an adhesive, the adhesive may be a polymericacidic composition formulated alone or with its associated ester.Solvent and tackifying agent may also be added to the adhesivecomposition to provide pressure sensitive adherent properties. Solventsof the adhesive can include, but are not limited to aqueous solvents,organic solvents, low volatility organic solvents, and inorganic fluids.In some embodiments, the solvent system is selected to provide: 1)adhesive properties; 2) low volatility (e.g., to avoid the negativeimpact of evaporation); 3) adequate solubilization of the polymeric acidcomposition; and 4) mobility and interaction with the color former andcolor developer composition without interfering with chromic transition.Tackifiers may also be added to added to ensure pressure sensitivecontact. Tackifiers of interest include, but are not limited tocarboxylated monoesters of polyglycols, etc.

The adhesive composition may also include a polymeric binder. Polymericbinders can be chosen from a large series of different polymers.Polymers may be soluble or alkali-soluble and compatible with the usedtackifier. Suitable water-soluble and alkali-soluble polymers are e.g.,polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, copolymersof acrylic acid with alkyl esters of acrylic or methacrylic acid whereinthe alkyl group comprises 1 to 4 carbon atoms such as methyl acrylateand n-butyl acrylate, with the proviso that the acrylic acid content isat least above 70% in the case of methyl acrylate and above 85% in thecase of n-butyl acrylate, further copolymers of maleic acid and e.g.ethylene, vinyl methyl ether and vinyl acetate,dimethylhydantoin-formaldehyde resin and polyethylene imine.

The polymerization of acrylic acid and methacrylic acid and thecopolymerisation of these acids with lower alkyl esters of acrylic acid(methyl, ethyl, butyl) may be carried out in solution in water, inmethanol or in mixtures of both according to known polymerisationtechniques, e.g. according to the methods described in Houben-Weyl,“Methoden der organischen Chemie”, Makromolekulare Stoffe, vol. 14/1,pages 1018-1021, Georg Thieme Verlag, Stuttgart (1961). Polymerisationmay also occur according to known methods in a non-solvent, whereby thepolymer formed precipitates out of solution. In the same way emulsioncopolymerisation techniques may be applied when mixtures are used ofacrylic acid or methacrylic acid with alkyl esters thereof, wherein theratio of acid component is relatively low (30 to 55% by weight).

The amount of polymeric binder present in the adhesive may vary widely,such as from 1% to 99% w/w, such as from 5% to 95% w/w, such as from 10%to 90% w/w, such as from 15% to 85% w/w, such as from 20% to 80% w/w,such as from 25% to 75% w/w, such as from 30% to 70% w/w, such as from35% to 65% w/w and including from 40% to 60% w/w.

In certain embodiments, the adhesive composition functions as both anadhesive and color developer. For example, adhesives of interest mayinclude those described above having a polyacrylic acid and associatedacid ester where the adhesive functions as both the developer and as apressure sensitive adhesive. In certain embodiments, adhesives may beTesafix™ 4965 (Tesa AG Quickbornstr, 24 D-20253 Hamburg Germany) andrelated adhesive tapes such as Tesafix™4972.

Where the adhesive composition functions as both an adhesive and colordeveloper, the amount of adhesive composition in the subject colorchange compositions may vary from 1% to 99% w/w, such as from 5% to 95%w/w, such as from 10% to 90% w/w, such as from 15% to 85% w/w, such asfrom 20% to 80% w/w, such as from 25% to 75% w/w, such as from 30% to70% w/w, such as from 35% to 65% w/w and including from 40% to 60% w/w.

In some embodiments, the subject color change compositions may alsoinclude one or more tackifying agents or resins. Hydrocarbon tackifiersof interest include petroleum based feedstocks made of one or more ofaliphatic tackifiers (C5, i.e., polymers composed of five-carbonaliphatic monomers), aromatic tackifiers (C9, i.e., polymers composed ofnine-carbon aromatic monomers), dicyclopentadiene (DCPD), or mixturesthereof. For example, the subject tackifying agents may include a C5/C9aliphatic/aromatic resin where the C5 tackifier is copolymerized witharomatic monomers.

Alternatively, tackifying agents may include polymers containing acidicside chains such as methacrylic acid, acryloyl chloride, acrylamineco-mixes, acrylate co-polymer admixes, sodium polyacrylate, propionicacid polymers, acryloyl groups, methacrylic acid derivatives,ethylacrylic acids, or mixtures thereof.

When present, the amount of tackifying agents in compositions of theinvention may vary depending on the particular color former and colordeveloper compositions, stimulus of color change, type of chromictransition, where in some embodiments the amount ranges from 0.0001% to99% w/w, such as 0.001% to 95% w/w, such as 0.01% to 90% w/w, such as0.1% to 85% w/w, such as 0.5% to 80% w/w, such as 1% to 75% w/w, such as5% to 70% w/w, such as 10% to 65% w/w and including 1% to 25% w/w.

The subject compositions may also include one or more modulating agentsor matrices. By “modulating” is meant a compound, layer or matrix that,when present, increases or decreases the rate of color formation by thecolor change composition, in some embodiments by facilitating thestability of encapsulation, migration or diffusion of one or both of thecolor former or color developer. Modulating agents and matrices may bepassive or active in functioning to offset, separate, control, modulate,accelerate, delay, attenuate, or predictably influence the interactionbetween color former and color developer.

In some embodiments, the modulating agent is an accelerating agent,which increases the rate of chromic transition by the color changecomposition. Accelerating agents may include compounds that facilitatethe breakdown of encapsulation, semi-encapsulation, migration, ordiffusion of one or both color developer or color former in response tothe applied stimulus. For example, the accelerating agent may decreasethe time required for chromic transition by 1 second or more, such as 2seconds or more, such as 5 seconds or more, such as 10 seconds or more,such as 30 seconds or more, such as 60 seconds or more, such as 5minutes or more, such as 10 minutes or more, such as 30 minutes or moreand including decreasing the time required for chromic transition by 60minutes or more.

In other embodiments, the modulating agent may be a decelerating agentwhich decreases the rate of chromic transition by the color changecomposition. Decelerating agents may include compounds that facilitatethe stability of encapsulation, semi-encapsulation, migration, ordiffusion of one or both color developer or color former upon exposureto the applied stimulus. For example, the decelerating agent mayincrease the time required for chromic transition by 1 second or more,such as 2 seconds or more, such as 5 seconds or more, such as 10 secondsor more, such as 30 seconds or more, such as 60 seconds or more, such as5 minutes or more, such as 10 minutes or more, such as 30 minutes ormore and including increasing the time required for chromic transitionby 60 minutes or more.

The exact composition, thickness or concentration of the modulatingagent or substrate may vary depending on the particular color former andcolor developer compositions, stimulus of color change and type ofchromic transition.

In some embodiments, the modulating agent is a modulating layerpositioned between the color former compound and color developercompound such as for example, films, adhesive layers, wax layers,diffusion layers, porous layers melting layers, high viscosity layerspositioned between the color former compound and color developercompound which is sufficient to block or delay the onset of colordevelopment. For instance, one or more blocking layers may be employedto provide a delay in chromic transition after exposure to the appliedstimulus for 1 second or longer, such as 5 seconds or longer, such as 10seconds or longer, such as 30 seconds or longer, such as 60 seconds orlonger and including 5 minutes or longer.

In certain embodiments, the modulating layer is a hydrocarbon layer. Inthese embodiments, the chromic transition occurs as the color developermigrates through the hydrocarbon layer and subsequently interacts withthe color former resulting in chromic transition.

Modulating agents and matrices of interest may include, but not limitedto waxes, acrylics, plastic resins, carboxy methyl cellulose (CMC),printing varnishes, hydrocarbon layers, nitrocellulose, paraffin,microcrystalline waxes, natural waxes, clay coatings, coating resins,tapes, non-developer containing adhesives, particulate,micro-particulate, thin metal layers, plastic film layers, dried proteinlayers, dried cellulosic layers, spray coated layers, surfactant layers,emulsifiers, membranes, semi-permeable membranes, filters, transparentlayers, compliant layers, sharp melting point mediums, long chainamines, long chain carboxylic acids, long chain weak acid donors, chargecarrying polymers, polymerize waxes, alkylated polymers, polyenes,polyolefins, polyethylene glycols, polypropylene glycols, clay coatings,and the like.

The subject color change compositions may also include one or morebuffering agents.

The term “buffering agent” is used in its conventional sense to refer toa solution of weak acid (and conjugate base) or weak base (an conjugateacid) that is employed to modulate the pH of a composition. Anyconvenient buffering agent may be employed, including but not limited tophosphate buffers (e.g., PBS), tris-buffers, citrate buffers (e.g.,sodium citrate), acetate buffers (e.g., sodium acetate) borate buffers(e.g., borax) and combinations thereof, among other buffering systems.For example, in certain instances the buffering agent is a two-componentbuffer of sodium phosphate and citric acid having a pH range from 3.0 to8.0.

The amount of buffering agent in compositions of the invention may varyranging from 0.0001% to 99% w/w, such as 0.001% to 95% w/w, such as0.01% to 90% w/w, such as 0.1% to 85% w/w, such as 0.5% to 80% w/w, suchas 1% to 75% w/w, such as 5% to 70% w/w, such as 10% to 65% w/w andincluding 1% to 25% w/w.

Color former and color developer compositions according to certainembodiments of the invention may also include one or more luminescent orfluorescent compounds. For example, luminescent compounds may includevisible as well as non-visible spectrum fluorescent dye compounds,chemiluminescent dye compounds as well as solvatoluminescent andhydroluminescent dyes compounds. Colors can be deeply enriched usingfluorescent and glow-in-the-dark or photo-luminescent pigments as wellas related color additives. For example, color can be obscured by an onecolor of a diacetylenic composition or other thermochromic dye such thatwhen a temperature triggering event occurs, the fluorescent signalbecomes visible when utilizing the corresponding wavelength to revealthe fluorescent dye composition. Luminescent compounds of interest mayinclude, but are not limited to fluorescein, fluoresceine,resourcinolphthalein, rhodamine, imidazolium cations, pyridoimidazoliumcations, dinitrophenyl, tetramethylrhodamine, among other types ofluminescent compounds.

The amount of luminescent agent in compositions of the invention mayvary, ranging from 0.0001% to 99% w/w, such as 0.001% to 95% w/w, suchas 0.01% to 90% w/w, such as 0.1% to 85% w/w, such as 0.5% to 80% w/w,such as 1% to 75% w/w, such as 5% to 70% w/w, such as 10% to 65% w/w andincluding 1% to 25% w/w.

Methods for Preparing Color Change Compositions

Aspects of the invention also include methods for preparing the subjectcolor change compositions. In some embodiments, methods for preparingthe color change compositions may be characterized by a first process ofproducing an a color former and color developer composition, whichincludes combining one or more color former compounds with one or morecolor developer compounds, and then a second process of producing thefinal color change composition by combining the color former and colordeveloper composition with an amount of a copolymer sufficient toeliminate background color of the color former and color developercomposition during transition from a first color state to a second colorstate. Additives can be incorporated into the subject compositionseither when producing the color former and color developer compositionor alternatively when combining the color former and color developercomposition with the copolymer.

In other embodiments the color change compositions are prepared bysimply combining the color former compound, color developer compound andcopolymer (and additives, where desired) simultaneously.

In certain methods, an amount of one or more color former compounds andan amount of one or more color developer compounds are mixed together,either with or without a solvent, to produce a color former and colordeveloper composition. Where a solvent is not employed, the colordeveloper compound may be in a molten state (i.e., liquid or melted) tofunction as a solvent such that the color former may be dissolveddirectly into the color developer compound. One or more additives (e.g.,tackifying agents, adhesives, luminescent dyes, etc.) may also be mixedinto the color former and color developer composition. Where a solventis employed, each additive may be separately dissolved in a solvent andthen added to the color former and color developer composition or theadditive may be added neat into the composition. Where a solvent is notemployed, each additive may be dissolved directly into the colordeveloper compound.

Where the color former and color developer composition is first producedbefore mixing with the copolymer, methods of the invention furtherinclude contacting an amount of the color former and color developercomposition with an amount of one or more of the subject copolymers thatare sufficient to eliminate background color of the color former andcolor developer composition during transition from the first color stateto the second color state. Depending on the physical state of thecopolymer, the copolymer may be combined with the color former and colordeveloper composition in molten form, dissolved in a solvent or as asolid (e.g., powder, granule, flake, etc.) Where the copolymer is in theform of a solid, the particle size of the copolymer may be reducedbefore mixing the components together. The particle size may be reducedby any convenient protocol and may include but is not limited to lumpbreakers, hammermills, fine grinders, classifier mills or sifters, amongother particle size reduction protocols. In certain embodiments, toreduce the particle size, the copolymer is a powder and is passedthrough a mesh screen. Depending on the particle size desired, the meshscreen may vary. In some embodiments, the mesh screen is a 2 mesh screenor smaller, such as a 4 mesh screen or smaller, such as a 10 mesh screenor smaller, such as a 20 mesh screen or smaller, such as a 30 meshscreen or smaller, such as a 40 mesh screen or smaller, and including a60 mesh screen or smaller.

In some embodiments, all of the components of the subject compositions(e.g., color former compound, color developer compound and any optionaladditives) are added to a mixer simultaneously. In other embodiments,each component may be added to a mixer sequentially. In certainembodiments, each component may be added to a mixer in a specific order.For example, in certain instances, methods include adding the componentsof the subject composition to the mixer in the order: 1) an amount ofsolvent, if present; 2) an amount of color developer (in molten form ifno solvent is employed); 3) an amount of color former; 4) copolymersufficient to eliminate background color of the color former and colordeveloper composition during transition from a first color state to asecond color state; and 5) any desired additives. In some embodiments,each of the components may be mixed concurrently while being added tothe mixer. In other embodiments, all components of the subjectcompositions are first added to the mixer and then the entirecomposition is mixed.

The subject color change compositions may be mixed by any convenientmixing protocol, such as but not limited to planetary mixers,Patterson-Kelley blender, hand mixers, standup mixers, inline mixers,powder liquid mixers, batch mixers, kneaders, agitator drives,impellers, hydrofoil mixers, aerators, among other mixing protocols.

In embodiments of the invention, the subject color change compositionsare mixed for an amount of time sufficient to incorporate each componentand to produce a homogenous mixture. For example, the color changecompositions may be mixed for 1 minute or more, such as 2 minutes ormore, such as 3 minutes or more, such as 5 minutes or more, such as 10minutes or more, and including 15 minutes or more.

In certain embodiments, the pH of the composition may be adjusted whilemixing the components of the color change composition. By adjusting thepH is meant the pH of the composition is either increased or decreased,as desired. In some embodiments, the pH of the composition is adjustedto have a pH which ranges from 3 to 10, such as 4 to 9, such as 4.5 to8.5 and including a pH of from 5 to 7. The pH of the composition may beadjusted using any convenient protocol. In some embodiments, the pH isdecreased by adding an acid (e.g., HCl). In other embodiments, the pH isincreased by adding a base (e.g., NaOH). In certain embodiments, the pHof the composition may be adjusted by adding a buffer to the any of thecomponents, such as by adding an amount of sodium citrate dihydrate.

The properties of the subject color change compositions or anyintermediate compositions produced during methods of preparing thesubject color change compositions may be characterized at any convenienttime. The term characterizing is used to refer to the analysis of one ormore of the properties and/or components of the subject color changecompositions or any intermediate compositions produced during methodsfor preparing the subject color change compositions. Characterizing mayinclude, but is not limited to, determining the pH, physical properties(e.g., solid density, water content), content assay (API), spectroscopicproperties, particle size distribution and impurity composition (tracemetals, relating substances, etc.). Methods for analyzing compositionsof the invention may include, but are not limited to the use of highperformance liquid chromatography (HPLC), gas chromatography, ionizationspectroscopy, among other types of analysis.

In some embodiments, methods of the invention also include assessing theproperties of the characterized composition. By “assessing” is meantthat a human (either alone or with the assistance of a computer, ifusing a computer-automated process initially set up under humandirection), evaluates the determined composition and determines whetherthe composition is suitable or unsuitable to continue on to the nextstep of preparation. If after assessing that the determined compositionis suitable, each composition may proceed to the following step withoutany further adjustments. In other words, methods of these embodimentsinclude a step of assessing the determined composition to identify anydesired adjustments.

In some embodiments, methods include monitoring each step in preparingthe subject color change compositions. In some embodiments, monitoringincludes collecting real-time data (e.g., pH, content assay, moisturecontent), such as by employing a detector to monitor each composition.In other embodiments, monitoring includes characterizing eachcomposition at regular intervals, such as every 1 minute, every 5minutes, every 10 minutes, every 30 minutes, every 60 minutes or someother interval.

After the components of the subject compositions are sufficiently mixed,a master batch may be produced. Master batches of the subjectcompositions may be formed into any convenient form, such as pellets,granules, powder, flakes, small discs, cubes, tiles, rods, ingots,slugs, sheets, sticks, blocks, dowels, cords, extruded shapes, tubes,balls, molded shapes, slab forms, pan shapes, casted shapes andbullions, among other forms of master batches. In some embodiments, aliquid (e.g., molten) master batch is produced. In other embodiments,master batches of the color change compositions are pelletized. In yetother embodiments, master batches of the color change compositions areshape molded into ingots, tubes, discs, sticks or other convenientshape. In still other embodiments, master batches of the color changecompositions are granulated. Where the subject compositions aregranulated, the color change composition master batch granules may beformed by milling the mixture of color former and color developercomposition and copolymer. By milling is meant, grinding or otherwiseprocessing the solid color change composition to reduce the particlesize of the dried composition. The composition may be milled by anyconvenient milling protocol, for example, round impellers, axial flowimpellers, radial flow impellers, ball mill, rod mill, autogenous mill,pebble mill, grinding rolls, buhrstone mills, semi-autogenous mill,vibratory mill or roller mill, among other protocols.

In certain embodiments, color change compositions of interest areprepared as a pseudo master batch. In producing a pseudo master batch ofthe subject compositions, a mixture of the components (e.g., colorformer and color developer) are combined as an aqueous slurry with anemulsifier and a powdered plastic resin. The aqueous slurry mixture isthen dried (e.g., by flash drying) to form a powder, granulate, flake orparticulate without the need to pelletize or shape mold the compositionto form a master batch.

Suitable emulsifiers for producing a pseudo master batch may be anyconvenient emulsifying agent, including but not limited to cationic,anionic or non-ionic emulsifiers, such as for example, diacetyl tartaricacid esters, acetic acid esters of monoglycerides, citric acid esters ofmonoglycerides, lactic acid esters of monoglycerides, mono- anddiglycerides, polyglycerol esters of fatty acids, polyglycerol,polyricinoleate, propylene glycerol esters of fatty acids, sorbitantristearate, sorbitan monostearate, among other types of emulsifyingagents.

Suitable powdered plastic resins for producing the pseudo master batchmay be any convenient thermoplastic composition or other type ofpolymeric plastic, including by not limited to polyvinyl chloride (PVC),various polyolefins such as polypropylene and polyethylene, high densitypolyethylene (HDPE), low density polyethylene (LDPE), cross-linkedhigh-density polyethylene (XLPE), softened acrylic, ABS, thick Kapton™tape materials, Teflon® (polytetrafluoroethylene (PTFE),tetrafluoroethylene TFE and fluorinated ethylene polypropyleneFEP)-based materials, brand names such as Kydex, polystyrene,thermoplastic polyesters, nylon, styrene-butadiene, epoxy casts,polybutylene, TPX (poly(methyl pentene), terephtalate polyethylene(PET), PETE, PETF, polyethylene teraphthalate G copolymer (PETG),polysulfone (PSF), polyurethane (PUR) Thermanox™ (TMX),polymethylmethacrylate, ethylenechlorotrifluoreethylene (ECTFE),ethylentetrafluorethylene (ETFE), polinvinylidene fluoride (PVDF),ethylene-propylene rubber (EPR), silicone rubber (SI), Alcryn®thermoplastic rubber (TPR), HT thermoplastic rubber (HTPR), Santoprene®thermoplastic rubber (TPR), LSOH cross-linked compounds, LSOHthermoplastic compounds, methylvinyletherfluoralkoxy (MFA),perflouroalkoxy (PFA), thermoplastic polyester elastomer (TPE),polyimide (Kapton®), polyurethane (PUR), polyvinyl chloride 105° C.(PVC), polyvinyl chloride 70° C. (PVC), low temperature polyvinylchloride (LTPVC), oil resistant Polyvinyl chloride (OR PVC), semi rigidpolyvinyl (SR PVC), polyvinyl chloride polyurethane (PVC PUR),copolyester (COPET, PCTA, PCTG), polycarbonate, styrene acrylonitrile(SAN), glycolised polyester terephthalate (glycolised polyester, PETG),styrene dutadiene copolymers (SBC), cellulose acetate propionate (CAP),and the like. By powdered is meant, at least in some instances, a solidsubstance reduced to a state of fine, loose particles by crushing,grinding, disintegration, etc.

In one example, a pseudo master batch may be produced by mixing anamount of a composition having a leuco dye, glycerol monostearatederivative and a copolymer of formula (I) described above:

as an aqueous slurry with an amount of an aqueous cationic polyethyleneemulsion and powdered polyethylene. After mixing the slurry to form auniform paste, the paste is spray dried in a drum dryer to produce alarge granulated pseudo master batch composition without the need forpelletization or shape molding.

In another example, a pseudo master batch may be produced by mixing anamount of a composition having a leuco dye, glycerol monostearatederivative and a copolymer of formula (II) described above:

as an aqueous slurry with an amount of an aqueous cationic polyethyleneemulsion and powdered polyethylene. After mixing the slurry to form auniform paste, the paste is spray dried in a drum dryer to produce alarge granulated pseudo master batch composition without the need forpelletization or shape molding.

In yet another example, a pseudo master batch may be produced by mixingan amount of a composition having a leuco dye, glycerol monostearatederivative and a copolymer of formula (IIII) described above:

as an aqueous slurry with an amount of an aqueous cationic polyethyleneemulsion and powdered polyethylene. After mixing the slurry to form auniform paste, the paste is spray dried in a drum dryer to produce alarge granulated pseudo master batch composition without the need forpelletization or shape molding.

Pseudo Master Batch Compositions

Pseudo master batch compositions, in some embodiments, are not limitedto the above-described color change compositions. Methods for preparingpseudo master batch compositions may, in certain embodiments, be used toprepare a wide range of different pseudo master batch compositions, suchas those described in greater detail below.

In certain embodiments, aspects of the invention include a method ofmaking a pseudo master batch composition by contacting an aqueouscomposition and a powdered plastic resin with a plasticizing emulsifierto produce a plasticized composition and flash drying the plasticizedmixture to produce a pseudo master batch composition. For example, theaqueous composition may be a slurry, such as a slurry which includes oneor more compounds that are microencapsulated. In some instances, theslurry includes a slurry of a color change composition, such as a dye,thermochromic compound, photochromic compound or a pigment. In oneexample the aqueous compositions include one or more leuco dyes, such astwo or more leuco dyes, such as three or more leuco dyes and including 5or more leuco dyes. In certain examples in preparing the subject pseudomaster batch compositions, the one or more leuco dyes aremicroencapsulated. The produced pseudo master batch composition, incertain instances, may be granulated, powdered or in the form of flakes.

The prepared pseudo master batch compositions according to someembodiments are homogeneous granulated or powdered compositions havingone or more non-plastic compounds, a plastic resin and a plasticizingemulsifier. In other embodiments, the pseudo master batch composition isa homogeneous granulated or powdered composition having a first plasticcomposition, a plastic resin and a plasticizing emulsifier.

Certain advantages to pseudo master batch include, but are not limitedto: cost reduction, lower pigment loading required, simplicity ofprocessing, direct conversion of an aqueous composition to a driedplastic powder in a single drying step, energy savings, the process canbe readily scaled from a laboratory bench level to a high-volumeproduction level, ease of direct extrusion to final plasticized masterbatch, compositions amenable to low extrusion temperatures, eliminationof heat stress for drying slurries, the process is amenable to a widerange of compositions, product applications, production formulations,and the like. In certain instances, pseudo master batch production isamenable to forward and reverse phase processing from hydrophobic tohydrophilic states; from hydrophilic to hydrophobic states and from onelike-kind state to another like-kind state.

In some embodiments, pseudo master batch compositions find use withtemperature sensitive materials, shear sensitive materials, andmaterials of non-like-kind nature that tend to separate on not dispersein alternate phases. For example, pseudo master batch compositions maybe applied in the preparation of sensitive and high value dye systemssuch as micro-encapsulated pigments, dyes, leuco dyes, fluorescent dyes,evanescent dyes, reversible and irreversible color change dyes, non-dyesystems and specialty chemistries such flavors, aromatic compositions,drugs, pharmaceuticals, topical materials, cosmetics, injestiblecompounds, fine reagents, biological materials, bio-pharmaceuticalmaterials and the like.

Slurries and emulsions can be used in mixing, compounding and dryingconditions provided by pseudo master batch production. For example,liquid based thermochromics, photochromics, fluorescent dyes, standarddyes, specialty dyes, optical shift agents, specialized pigments, lakedyes, micro-encapsulated pigments, specialty chemicals, organic andinorganic compounds and materials, low or high value additives, and thelike may be compounded under pseudo master batch processing conditions.

Often there are disadvantage to common slurry drying systems such as:agglomeration, caking, agglutination, crusting, the formation of hardgranulated materials that then need subsequent dispersion, heat stressto sensitive materials, oxidation, contamination, lengthy and costlyprocessing steps, and generally a lack of protection from degradation ofsensitive materials. Pseudo master batch processing by comparisonprovide an instant transition form one state to a second state in singlemixing and drying step. The process provides a compounded end productthat can be readily utilized and processed in subsequent productionmethods intended for the end products. By way of example, notlimitation, color change leuco dyes can be directly converted from anaqueous slurry to a plasticized powder or pellet that can be directlyutilized in plastics engineering. Standard method of drying andprocessing leuco dye slurries require high temperature drying methods,multiple steps, re-suspension and dispersion and often re-heating andcompounding until they are suitable for use. Standard method of leucodye drying and compound can lead to significant losses in colorintensity and performance compared to pseudo master batch processing.The end result of pseudo master batch production provides a means to uselower concentrations of costly materials combined with a lower costproduction methods that can dramatically reduce pricing and increaseperformance by comparison.

In certain embodiments, aspects of the present invention include amethod of making a leuco-dye pseudo master batch composition bycontacting an aqueous leuco dye composition and a powdered plastic resinwith a plasticizing emulsifier to produce a plasticized leuco dyecomposition and flash drying the plasticized leuco dye composition toproduce a leuco dye pseudo master batch composition. For example, theaqueous leuco dye composition composition may be a slurry, such as aslurry which includes one or more leuco dyes that are microencapsulated.In one example the aqueous compositions include one leuco dye or more,such as two or more leuco dyes, such as three or more leuco dyes andincluding 5 or more leuco dyes. In certain examples in preparing thesubject pseudo master batch compositions, the one or more leuco dyes aremicroencapsulated. The prepared pseudo master batch composition, incertain instances, may be granulated, powdered or in the form of flakes.For example, in certain embodiments the prepared pseudo master batchcomposition may be a homogeneous powdered leuco dye-plastic resin pseudomaster batch composition having one or more leuco dyes, a plastic resinand a plasticizing emulsifier.

In general pseudo master batch finds direct and relevant utility toplastics extrusion and injection molding with or without postpelletizing the final composition. The granular nature of pseudo masterbatch along with it density that is in close proximity to the density ofmany key resins used in the plastics industry, allow it to be directlyused in combination with plastics during the injection molding process,extrusion process, blow molding process, compression molding process orany of a variety of processes utilized in the plastics industry.

By contrast, pseudo master batch processing also lends itself toreducing cost and increasing value to low value high volume recyclablematerials such as wood, plastics, metals, minerals, rock, and othergenerally disposable commodities. In certain embodiments, methods forpreparing pseudo master batch composition can used to rapidly recycleand utilize materials that are often too costly and difficult tore-utilize.

Certain food, drug, and cosmetics may also be prepared as a pseudomaster batch composition. For example, food colors, flavors, andadditives that are often difficult to dry, sensitive to high heats andoxidation, and are not physically or chemically compatible can beprepared as a pseudo master batch. In certain instances, dry beveragebased additives, flavors and colors intended for rapid dispersion intoliquids can be prepared as a pseudo master batch composition.

The exact and final concentration will vary depending on the desiredloading of the pseudo master batch component of interest. In the eventthat powder forms of pseudo master batch compositions are used directlywith plastic resins the pseudo master batch composition may be presentat a final concentration from between 0.5% and 50% by weight of theplastic resin used for making a certain plastic article, such as from 1%to 25% by weight, and including in the range of 2.5% to 10% by weight.

The addition of pseudo master batch as a powder directly to a plasticresin to be processed can be facilitated and assisted by first priorcoating the plastic carrier resin with an oil or coating compositionthat improves adherence of the powdered pseudo master batch to thecarrier resin of interest. For example mineral oil can be used to coatpolyethylene of polypropylene with a thin adherent film that bindsubsequently added powdered pseudo master batch. The combined mixturecan be easily tumbled to uniformly coat the plastic resin pellets withthe pseudo master batch. The final mixture can be added plasticsprocessing equipment hoppers and the like and directly utilized forproduction.

Oil and or adherent coatings can range from 0.01% to 50% by weight, suchas in the range from 0.1% to 25% by weight, such as in the range from0.2% to 10%, and including in the range from 0.5% to 5% by weight.Depending on the coating properties, final concentration of pseudomaster batch utilized, resin particle dimensions, and the materialprocessing parameters utilized to make the plastic article of finalinterest.

Oil and adherent coatings can include, but are not limited to mineraloils, mineral oils of different molecular weight cut-offs, silicon oils,long chain fatty acids, lipids, lubricating oils, liquid hydrocarbons,emulsifying oils, natural oils, vegetable oils, nut oils, liquid waxes,glycerol, long chain alcohols, commercial petroleum oils and pastes, lowmolecular weight oils, pure oils, mixed oil systems, low viscosityand/or high viscosity oils and the like. The type of oil used as anadherent coating will depend on the application of interest, the pseudomaster batch applications and general composition to be deployed.

In certain embodiments, pseudo master batch compositions of interest areprepared from: photochromic slurries, fluorescent slurries, other waterbased emulsions that have application to pelletized additives used forinjection molding or extrusion including, tagging agents, anti-slipagents, anti-oxidants, UV inhibitors, anti-static agents, foamingagents, blow agents, optical agents, various plastic colorants and thelike.

In some embodiments, plastics applied as pseudo master batch areconverted to a powdered master batch or to a palletized concentratedmaster batch. The conversion can be accomplished any convenientpalletizing protocol. For example, the plastic pseudo master batch beprepared as plastic pellets by strand extrusion and high speed cutting.In some instances, the strand extrusion method involves air cooling orwater cooling the strands prior to cutting. Alternatively, alternatepalletizing process can be utilized such as water ring palletizing orfront surface air cooling palletizing.

Due to the pigment protective nature of the pseudo master batch a widerange of palletizing process can be utilized. For example, as analternative to more standard palletizing processes, pseudo master batchcan be melted in a continuous format into sheets, beads, and othergeometries. The process can involve integrated steps such as dryingpseudo master batch followed in-line by melting the master batch,cooling and setting a particular geometric shape of the final mixture,and finally followed by possibly cutting or crushing the finalparticulate or collecting in a set shape.

In certain embodiments, the protective nature of the pseudo master batchprocess provides for a variety of implementation means for utilizing itas concentrate additive in a wide arrange of different processingmethods. The surfactant post encapsulation and dispersion of aparticular agent of interest incorporated into pseudo master batchenables the agent to be well protected under hash or severe processingconditions such as plastics extrusion or plastics injection molding. Insome instances, pseudo master batch processing provides a protectiveextra encapsulation process that further ensures optimal protection anddistribution/dispersion of technical agents with in a matrix. In someinstances, methods of interest include making an emulsified slurrycomposition by contacting an aqueous slurry having one or moremicroencapsulated compounds with a powdered hydrophobic composition anda plasticizing emulsifier to produce plasticized composition and dryingthe plasticized composition to produce a plasticized slurry compositionhaving one or more microencapsulated compounds. For example, themicroencapsulated compound may be a color change compound as describedherein, such as one or more leuco dyes. In other instances, methodsinclude a method of making a pseudo master batch composition bycontacting a hydrophilic composition and a hydrophobic composition witha plasticizing emulsifier to produce a plasticizedhydrophilic-hydrophobic composition and flash drying the plasticizedhydrophilic-hydrophobic composition to produce a pseudo master batchcomposition. For example, the hydrophilic compound may be a woodcomposition, ceramic composition, color change composition or otherhydrophilic composition as described in greater detail below. Likewise,the hydrophobic composition is, in certain instances, a plasticcomposition, such as a plastic resin including, but not limited to:polyvinyl chloride (PVC), various polyolefins such as polypropylene andpolyethylene, high density polyethylene (HDPE), low density polyethylene(LDPE), low linear density polyethylene (LLDPE), homo-polymerpolyethylene (HPPE), polypropylene (PP), linear polypropylene (LPP),homo-polymer PP (HPP), cross-linked high-density polyethylene (XLPE),ethyl vinyl acetate (EVA), EVA's with different vinyl acetateconcentrations, softened acrylic, ABS, thick Kapton™ tape materials,Teflon® (polytetrafluoroethylene (PTFE), tetrafluoroethylene TFE andfluorinated ethylene polypropylene FEP)-based materials, brand namessuch as Kydex, polystyrene, thermoplastic polyesters, nylon,styrene-butadiene, epoxy casts, polybutylene, TPX (poly(methyl pentene),terephtalate polyethylene (PET), PETE, PETF, polyethylene teraphthalateG copolymer (PETG), polysulfone (PSF), polyurethane (PUR) Thermanox™(TMX), polymethylmethacrylate, ethylenechlorotrifluoreethylene (ECTFE),ethylentetrafluorethylene (ETFE), polinvinylidene fluoride (PVDF),ethylene-propylene rubber (EPR), silicone rubber (SI), Alcryn®thermoplastic rubber (TPR), HT thermoplastic rubber (HTPR), Santoprene®thermoplastic rubber (TPR), LSOH cross-linked compounds, LSOHthermoplastic compounds, methylvinyletherfluoralkoxy (MFA),perflouroalkoxy (PFA), thermoplastic polyester elastomer (TPE),polyimide (Kapton®), polyurethane (PUR), polyvinyl chloride 105° C.(PVC), polyvinyl chloride 70° C. (PVC), low temperature polyvinylchloride (LTPVC), oil resistant Polyvinyl chloride (OR PVC), semi rigidpolyvinyl (SR PVC), polyvinyl chloride polyurethane (PVC PUR),copolyester (COPET, PCTA, PCTG), polycarbonate, styrene acrylonitrile(SAN), glycolised polyester terephthalate (glycolised polyester, PETG),styrene dutadiene copolymers (SBC), cellulose acetate propionate (CAP),and the like. In some embodiments, the hydrophilic composition is a woodcomposition and the hydrophobic composition is a polyethylene orpolypropylene resin. In certain instances, the wood composition may bean aqueous wood slurry, dampened wood powder or dry wood powder.

Pseudo master batch production and applications can range over a varietyof compounds, compositions, physical types, and chemical properties. Byway of example, not limitation, pseudo master batch can be used forprocessing material with different properties including: hydrophiliccompounds into hydrophobic environments; hydrophilic compounds intohydrophilic environments; hydrophobic compounds into hydrophilicenvironments; hydrophobic compounds into hydrophilic environments;aqueous pseudo master batch; solvent based pseudo master batch dryingand processing and the like. The exact composition and formulation forpseudo master batch processing will depend on the material properties ofinterest and the intended application of interest.

Candidate Materials for Pseudo Master Batch and Concentration Ranges:

Technical agents and additives suitable for incorporation and dispersioninto pseudo master batch include, but are not limited to: thermochromicslurries and compounds, photochromic slurries and compounds, fluorescentdye slurries, IR dye slurries, security dyes, technical componentslurries and encapsulated slurries, re-cycled or re-processedwood-plastic composition for plastic wood extrusion, water and oil basedflavors and aromatic compounds, security dyes for adding to plastics,tagging agents for identifying a particular processors product, variousmicro-encapsulated compounds, none micro-encapsulated compounds,anti-bacterial compounds, shear sensitive materials, calcium carbonateand fillers, pearlescent materials, glow-in-dark pigments, slow releasenutritional compounds, slow release pharmaceutical compounds, vaccinecomponents, drug delivery components, industrial agents and components,blow agents for foamed expansion, sensitizing agents and components,technical organic compositions, accelerated bio-degradable additives,food starch and polylactic acid (PLA), coffee concentrates, teaconcentrates, ceramic micro-spheres, tagging agents for security,dissolving and dispersing agents, anti-fungal agents, deodorantcompositions and agents, sunscreen additives, absorbent compounds forlitter boxes, oral sensitizing compounds, color stabilizing compounds,evanescent micro-encapsulated compounds, optical brighteners, YAG, CO2and other laser marking additives, and the like.

Pseudo master batch can be used for a range of technical, non-technical,sensitive, industrial, commercial and other additive applications. Forexample, areas of application may include, but are not limited to:compounding for industries, pharmaceuticals and drugs, industrialprocessing, production of house hold and consumer products, food andbeverage-concentrates for dispersion and addition, cosmetics anddermatologic applications, coatings and paint, the recycling industry,wood-plastic compositions, environmentally friendly products wheredispersion of recycled materials will find use, composites that enablethe dispersion of non-like-kind materials, plastic-mineral compositions,a wide range of micro-encapsulation products and the like.

General Technical Agents and Additives to Pseudo Master Batch Pre andPost Processing:

A wide range of additives can be included in the final formulation of aparticular master batch derived from the pseudo master batch process.Additives can be included depending on the final formulation, intendeduse, improved qualities of the final product, function of the finalproduct, processing characteristics during manufacturing and the like.For example, additives can include, but are not limited to: ethylene bisstearamide as a protective lubricant, anti-caking agents to reduce buildup at dies and during processing, anti-static agents to reduce thecomplications of static, anti-oxidants to reduce oxidation andaccelerated aging, other lubricants to improve processability, fillersto improve performance and reduce cost of goods, dispersing agents toimprove active agent dispersion into matrices, various optical agentsand stationary colors and the like.

Pseudo Master Batch Mixing Processes:

Wet/damp components of pseudo master batch can be mixed in a variety ofconventional commercial and industrial mixing units. By way of example,not limitation, commercially available mixing units can include: doughmixers, mortar mixers, cement mixers, blade mixers, ribbon mixers andthe like. In embodiments, mixing is thorough and ensures that anyparticulate achieves full coating and uniformity with a particularemulsifying agent. It is desirable to utilize a continuous mixingprocess where ingredients can be added sequentially and that the mixingprocess can be maintained during the addition steps. Likewise, it isrelevant to utilize mixing processes where loading and unloading areconvenient and efficient.

Pseudo Master Batch Drying Processes:

Pseudo master batch drying processes can be utilized that are efficientfor water content from 10% by weight to 80% by weight, such as rangingfrom 15-40% by weight. Drying process can include by way of example, notlimitation: static drying using commercial drying vats or reactors,static rack drying with continuous air flow, spary drying oratomization, fluid bed drying, levitated fluid bed drying,through-material forced air bed drying, conveyor drying, oven drying,convection oven drying, furnace drying, IR lamp drying, radiation heatdrying, freeze drying, powder drying processes, tumble drying, forcedair drying, and the like. Drying can include injected heat, variableheating levels, variable forced air volumes (cubic feet per minute).

In some embodiments, due to the damp low density congealed nature ofcertain pre-mixed pseudo master batch compositions, the moderate watercontent, and the large surface area resulting from the presence of thepowderized plastic resin-carrier, through-material forced air bed dryingprocesses may be used. For example, batch volumes of mixed pseudo masterbatch can be loaded into a through-material dryer and dried within 1-6hours. In some instances, through-material drying can be accomplishedwithin 1.5-2.5 hours, resulting in an efficient high throughputmanufacturing process. In certain instances, by injecting hot air intothe drying unit and incorporating in-unit heaters, a temperature risecan be achieved from room temperature to over 100° F. Additionally,certain through-material dryers permit uniform air volumes to be forcedthrough the pseudo master batch material. Likewise, since certain pseudomaster batch compositions are trapped and held in a specified space,loading, drying, clean-out, and repetition is extremely efficient.

One suitable through-material forced air dryer can be constructed havinga closed off chamber equipped with a high volume blower (2,000 to over8,000 cubic feet per minute). The dimension for the chamber can be abase of 40×40 inches squared and 40-45 inches tall. To improve energyefficiency and insulation, the chamber can be made with wood, aninsulating layer on metal, or an insulating plastic. The top is openwith a slot to slide in open-meshed drying screens for air to travelthrough. Heaters can be placed externally to the blower to inject hotair into the blower and internally to the chamber to increasecirculating air temperature within the chamber. Slots in the top theopen chamber provide a convenient means to slide in a drying screen. Thedrying screen's outer dimensions match the slot to ensure a tight fit.The drying screens come in pairs. The lower screen is equipped with sidewalls for to place and hold moist pseudo master batch. The lower screenalso has a rubberized seal to mate and seal with a second upper screenof the same dimensions. The upper screen also has a rubberized seal toensure complete seal air-tight around the two screens when they arestacked. The lower screen is installed at the top of the chamber.

A volume of pseudo master batch is placed on the lower screen toentirely fill the screen to the brim of the side-walls. The secondscreen is placed parallel and on top of the first screen and pseudomaster batch. The pseudo master batch is trapped and contained betweenthe laminating screens such that air can only be transported through themaster batch material. The upper screen is secured with straps, bolts,cords, or latches to ensure that the sandwiched screens and pseudomaster batch are fully secured. Once secured, the blower can beactivated so that air entering the chamber is forced vertically up andonly through the open mesh of the bottom containing screen, through themoist pseudo master batch material, and exits the upper open meshscreen. Upon activation of heaters, pseudo master batch is can beconveniently dried within a 2 hour period.

Due the low drying temperatures employed and high air volume passagethrough the pseudo master batch matrix, no burning, browning, shearing,there is no degradation of the material properties of the pseudo masterbatch induced by the drying process. Cleaning and replacement of pseudomaster batch in the drying unit is convenient as a result of the simplechamber construction.

Drying screen meshes for through-material forced air dryers can rangefrom 60 mesh to 390 mesh, such as in the range from 100 mesh to 300 meshand including in the range of 150 mesh to 250 mesh. Mesh materials canbe made with stainless steel or a plastic fiber (nylon or polyester).

Pseudo Master Batch Plastic Resins:

Where rapid and uniform agent dispersion in a plastic pseudo masterbatch composition is desired, a powder-granulated form of a plasticmatrix-carrier resin can be employed. Powderized plastics find use inrotational molding and other related processes where it is useful torapidly melt and disperse agents in a processed plastic. Likewise,pseudo master batch compositions benefit from the small particulategranular nature of carrier resins due to the large surface area forexposure and small particle size closer to pigment particle sizes. Insome embodiments, suitable palletized resin may range in size from 2millimeters to 5 millimeters in diameter. Pulverized plastic powder androtational molding resin granules can be specified to range in size from1 micron to 1 milimeter, such as in the range of 5 microns to 500microns and including in the range of 10 microns to 250 microns.

The final particle size and desired distribution will depend on thefinal application of interest and compatibility with the technicalagents of interest to be incorporated in to the corresponding pseudomaster batch formulation. In certain embodiments, the small granularnature of pulverized plastic powders provide particle sizing within arange that facilitate rapid incorporation of a technical agent into aplasticized environment facilitated by the emulsification andhomogenized mixing of a compatible surfactant.

Powderized granulated plastic carrier resins can include, but are notlimited to any convenient thermoplastic composition or other type ofpolymeric plastic, such as for example to polyvinyl chloride (PVC),various polyolefins such as polypropylene and polyethylene, high densitypolyethylene (HDPE), low density polyethylene (LDPE), low linear densitypolyethylene (LLDPE), homo-polymer polyethylene (HPPE), polypropylene(PP), linear polypropylene (LPP), homo-polymer PP (HPP), cross-linkedhigh-density polyethylene (XLPE), ethyl vinyl acetate (EVA), EVA's withdifferent vinyl acetate concentrations, softened acrylic, ABS, thickKapton™ tape materials, Teflon® (polytetrafluoroethylene (PTFE),tetrafluoroethylene TFE and fluorinated ethylene polypropyleneFEP)-based materials, brand names such as Kydex, polystyrene,thermoplastic polyesters, nylon, styrene-butadiene, epoxy casts,polybutylene, TPX (poly(methyl pentene), terephtalate polyethylene(PET), PETE, PETF, polyethylene teraphthalate G copolymer (PETG),polysulfone (PSF), polyurethane (PUR) Thermanox™ (TMX),polymethylmethacrylate, ethylenechlorotrifluoreethylene (ECTFE),ethylentetrafluorethylene (ETFE), polinvinylidene fluoride (PVDF),ethylene-propylene rubber (EPR), silicone rubber (SI), Alcryn®thermoplastic rubber (TPR), HT thermoplastic rubber (HTPR), Santoprene®thermoplastic rubber (TPR), LSOH cross-linked compounds, LSOHthermoplastic compounds, methylvinyletherfluoralkoxy (MFA),perflouroalkoxy (PFA), thermoplastic polyester elastomer (TPE),polyimide (Kapton®), polyurethane (PUR), polyvinyl chloride 105° C.(PVC), polyvinyl chloride 70° C. (PVC), low temperature polyvinylchloride (LTPVC), oil resistant Polyvinyl chloride (OR PVC), semi rigidpolyvinyl (SR PVC), polyvinyl chloride polyurethane (PVC PUR),copolyester (COPET, PCTA, PCTG), polycarbonate, styrene acrylonitrile(SAN), glycolised polyester terephthalate (glycolised polyester, PETG),styrene dutadiene copolymers (SBC), cellulose acetate propionate (CAP),and the like.

In certain embodiments, fluorescent pigments and slurries that can beprepared as pseudo master batch compositions. For example, certainfluorescent slurries may include fluorescent pigments such as SPL-11JAurora Pink, SPL-12J, Neon Red, SPL-13J Rocket Red, SPL-14J Fire Orange,SPL-15J Blaze Orange, SPL-17J Saturn Yellow, SPL-21J Corona Magenta.Formaldehyde free version include: SPL-11N Aurora Pink, SPL-13N RocketRed, SPL-14N Fire Orange, SPL-15N Blaze Orange SPL-17N Saturn Yellow,SPL-18N Signal Green, SPL-19N Horizon Blue, SPL-21N (GS) Corona MagentaSPL-25N, Horizon Blue (RS), and SPL-594N Invisible Blue. Finegrind/particle size fluorescent pigments include: EC-594 Invisible Blue,ECX-11 Aurora Pink, ECX-13 Rocket Red, ECX-15 Blaze Orange, ECX-17Saturn Yellow, ECX-18 Signal Green, ECX-19 Horizon Blue, ECX-20 PlutoPurple, ECX-21 Corona Magenta, and ECX-34 Strong Saturn Yellow.

In other embodiments, other colorants may be prepared into a pseudomaster batch composition, such for example AIT Colorants AqueousIn-Plant Tinting, Fluorescent Water Dispersions, HI-TINT Dispersions,NVC Colorants, Omni Tint, Phantom Water Dispersions Invisible YellowAIT-4466, Plast-E-Tint (PET) Conventional Dispersions, Plast-E-Tint(PET) Fluorescent Dispersions, SPLASH Colors-Pantone Blends, SPLASHColors SPL-J Dispersions, AIT118 White Dispersion, AIT222 Toluidine RedDispersion, AIT244 Red Iron Oxide (YS) Dispersion, AIT254 QuinacridoneRed Dispersion, AIT334 DNA Orange Dispersion, AIT364 Yellow OxideDispersion, AIT374 Permanent Medium Yellow Dispersion, AIT385 BrilliantYellow G Dispersion, AIT389 Hansa Yellow HS Dispersion, AIT421 BrownIron Oxide Dispersion, AIT434 Raw Umber Dispersion, AIT444 Burnt SiennaDispersion, AIT454 Burnt Umber Dispersion, AIT544 Phthalo Green BSDispersion, AIT644 Phthalo Blue RS Dispersion, AIT648 Ultramarine BlueDispersion, AIT684 Carbazol Violet Dispersion, AIT734 NF Black(Non-Flaking) Dispersion, AIT744 Lampblack Dispersion and the like.

In certain embodiments, filler materials are prepared as a pseudo masterbatch composition. For example, plastic, wood, plant matter, leaves,pine needles, construction site reclamation, paper, soil, landfill,sand, cement, concrete, asphalt, rubber, used, tires, rock, oil,calcium, metals. ceramic, glass, food stuffs, crop waste, silt, generalgarbage, waste from printing processes, general fillers, computer waste,consumer product waste, compost waste matter, landfill waste matter,rubbish, road-side waste, ocean pollution, used oils, rubber, recycledplastics, filtered waste, highly 100% proven sterilized medical waste,100% proven sterilized waste matter, fabrics, news papers, magazines,and the like can be utilized alone or in combination aspulverized/powderized fillers in the pseudo master batch process. One ormore filler composition can be used in combination with an emulsifierfor creating a common amalgamation or admixture and a plastic componentfor binding in the final pseudo master batch composition. In certainembodiments, methods of interest include making a pseudo master batchfrom recycled materials, such as recycled wood, cement, concrete, paper,plastics, among other types of recycled materials, by contacting acomposition having one or more granulated recycled materials and apowdered plastic resin with a plasticizing emulsifier to produce aplasticized recycled material composition and flash drying theplasticized recycled material composition to produce a pseudo masterbatch composition of one or more recycled materials. In someembodiments, a pseudo master batch composition of one or more recycledmaterials of interest includes recycled wood, such as recycled woodstirrers. In other embodiments, a pseudo master batch composition of oneor more recycled materials of interest includes recycled glass, such aspulverized glass bottles.

Dyes, pigments, blocking agents, aroma inducing compositions, opticalagents, and/or a variety of other additives can be added in the pseudomaster batch manufacturing process to ensure the final desired effect ofthe multi-element compounded material. Additives will be utilized at aspecific and determined concentration to generate the final physicaland/or chemical compounded material.

Sterilization processes can be employed to ensure that final pseudomaster batch compositions are suitable for selected food grade andrelated applications. By way of example, UV, gamma irradiation, solarirradiation, 200° C. or above temperature exposures at correspondingdwell times, possible addition of anti-microbial agents if required,dehydration, high pressure sterilization, freeze fracturing, high sheer,and/or a combination of parameters can be utilized as commercialprocess.

Depending on the utility and application of use, caution will need to betaken to ensure the traceability and contamination free level ofadditive is maintained. By way of example, not limitation, recycled orvested materials to be utilized for a particular application should be:none radio active, non-carcinogenic, sterilized, non-heavy metalcontaining, non-phthalates, and the like.

In some embodiments, pseudo master batch compositions are prepared witha plasticizing emulsifier. In certain embodiments, the plasticizingemulsifier is present in an amount sufficient to promote a commonsurface characteristic for none like-kind materials and substances toco-exist. In some embodiments, plasticizing emulsifying agents whendried, are present in an amount sufficient to enhance the cohesiveinteraction between a final plastic matrix comprising the endmulti-component composition. In certain instances, the emulsifying agentis present at a concentration that when coated on a mass of mixedparticulate, dominates the surface characteristics of the varyingparticulate types to a more homogenous and common processing state.Emulsifying agents can be neutral or charged. Charged emulsifying agentscan be cationic or anionic. Solids and active agents in an emulsifyingformulation can be of use in the emulsion from concentration from lessthan 0.1% to over 50% by weight in a solution, such as from between 1%to 50% and including from 5% to 35%.

A wide range of aqueous emulsions can be utilized in compounding andprocessing pseudo master batch. Emulsion selection will depend on thefinal application of interest, what technical material is to be utilizedin the formulation of interest, the characteristics and synergy betweenthe additives and agents utilized, and a variety of processingconditions. Emulsions is present in the subject pseudo master batchcompositions, in certain instances in an amount of from 0.1% to 50% byweight of the final pseudo master batch composition, such as from 0.5%and 40% by weight, such as from 1% to 30% and including from 10 to 25%by weight of the final pseudo master batch composition.

Example emulsions may include, but are not limited to: Michem® Emulsion09625: Cationic ethylene acrylic acid emulsion, Michem® Emulsion 09730:Cationic polyethylene emulsion, Michem® Emulsion 11226: Cationicpolypropylene emulsion, Michem® Emulsion 1270: Slip and anti-blockadditive, Michem® Emulsion 13025: Slip and anti-block additive, Michem®Emulsion 18325: Nonionic polyethylene wax emulsion, Michem® Emulsion21030: Anionic polyethylene emulsion, Michem® Emulsion 21930: AnionicTung Oil emulsion, Michem® Emulsion 24414: Anionic camauba wax emulsion,Michem® Emulsion 27720: Nonionic slip and anti-block additive, Michem®Emulsion 28640: Cationic polypropylene emulsion, Michem® Emulsion 29730:Nonionic polyethylene emulsion, Michem® Emulsion 32535: Nonionic,polyethylene emulsion, Michem® Emulsion 34935: Anionic paraffin/ethyleneacrylic acid wax emulsion, Michem® Emulsion 36840: Anionicparaffin/polyethylene wax emulsion, Michem® Emulsion 37135: Nonionicpolyethylene emulsion, Michem® Emulsion 39235: Nonionic high densitypolyethylene emulsion, Michem® Emulsion 41740: Nonionic, polyethyleneemulsion, Michem® Emulsion 42035A: Cationic water based emulsion ofpolyolefin waxes, Michem® Emulsion 43040: Nonionic polypropyleneemulsion, Michem® Emulsion 43240: Polypropylene emulsion, Michem®Emulsion 44730: Nonionic ethylene acrylic acid copolymer, Michem®Emulsion 45745P: Nonionic Polyethylene wax emulsion, Michem® Emulsion47950: Nonionic paraffin emulsion, Michem® Emulsion 48040M2: Nonionicmicrocrystalline wax emulsion, Michem® Emulsion 48625M1: Polymersolution, Michem® Emulsion 51715: Nonionic wax emulsion blend, Michem®Emulsion 52137: Nonionic polyethylene emulsion, Michem® Emulsion 52830:Anionic polyethylene wax emulsion, Michem® Emulsion 53145: Nonionicco-emulsion, Michem® Emulsion 61222: Water based emulsion of montanbased ester wax, Michem® Emulsion 61335: Anionic polyethylene emulsion,Michem® Emulsion 62330: Anionic paraffin/polyethylene emulsion, Michem®Emulsion 65140: Nonionic polypropylene emulsion, Michem® Emulsion 65435:Nonionic ethylene acrylic acid emulsion, Michem® Emulsion 66035: Anionicparaffin/polyethylene wax emulsion, Michem® Emulsion 70750: Anionicscale wax emulsion, Michem® Emulsion 71150: Anionic scale wax emulsion,Michem® Emulsion 71731MOD: Anionic paraffin emulsion, Michem® Emulsion72040: Nonionic polyethylene wax emulsion, Michem® Emulsion 73950:Cationic paraffin emulsion, Michem® Emulsion 79535: Nonionicpolyethylene/polypropylene blend, Michem® Emulsion 80939M: Nonionicparaffin wax emulsion, Michem® Emulsion 91240: Nonionic polyethyleneemulsion, Michem® Emulsion 91240G: Nonionic polyethylene emulsion,Michem® Emulsion 91735: Nonionic polypropylene emulsion, Michem®Emulsion 91840: Nonionic HD polyethylene/paraffin wax emulsion, Michem®Emulsion 93135M: Nonionic polyethylene emulsion, Michem® Emulsion 93235:Nonionic polyethylene emulsion, Michem® Emulsion 93335: Nonionicpolyethylene emulsion, Michem® Emulsion 93935, Nonionic polyethyleneemulsion, Michem® Emulsion 94340, Nonionic polypropylene emulsion,Michem® Emulsion 98040M1, Nonionic Fischer Tropsch wax emulsion Michem®,and Emulsion D310 Anionic polyamide dispersion.

The subject pseudo master batch compositions possess amenable processingtemperatures, strength of adhesive and cooperative binding, a transitionstate from a heated fluid state to a solid cooled state, adjustablecharacteristics such as adjustable melt-flow indexes, strength andstructural integrity in the solid state, good flow characteristics forplastics processing such as extrusion and injection molding, surfacetexturing and modifications for attractive end finishes, polishing, highcapacity for inclusion of foreign particulate, ease of coloring andtinting for various applications and the like.

Colorants, dyes, tinting agents, optical agents, surface effect pigmentsand the like can be utilized to convert the appearance of the finalpseudo master batch amalgamation to a an attractive and desirablefixture or article. For example, a wood-plastic stir stick can becompounded completely of recycled materials of foreign origin usingpseudo master batch processing and yet be colorized, extruded andfinished to resemble a wooden stir stick or alternatively a pure plasticstir stick. The exact visual appearance or coloration can be compensatedfor during the pseudo master batch process.

In some embodiments, methods interest include making a wood-plasticpseudo master batch composition by combining a wood composition and apowdered plastic resin with a plasticizing emulsifier to produce aplasticized wood-plastic resin composition; and flash drying theplasticized wood-plastic resin composition to produce a wood-plasticpseudo master batch composition. For example, the wood may be an aqueouswood slurry, a dampened wood composition or a dry wood powder. Wood maybe of any convenient type of wood depending on the wood-plastic pseudomaster batch composition desire. For example, suitable types of wood mayinclude, but is not limited to pine, cedar, celery-top pine, cypress,Douglas-fir, European yew, fir, hemlock, Huon pine, kauri, nutmeg-yew,larch, red cedar, redwood, cherry, rimu, sprice, sugi, white cedar,Nootka cypress, abachi, African padauk, afzelia, agba, alder, Americanchestnut, ash, aspen, ayan, balsa, basswood, beech, birch, blackbean,black tupelo, blackwood, boxelder, boxwood, Brazilian walnut,Brazilwood, bubinga, buckeye, butternut, bay laurel, camphor, carapa,catalpa, Ceylon satinwood, coachwood, cocobolo, corkwood, cottonwood,cucumbertree, dogwood, ebony, elm, eucalyptus, crabapple, pear,greenheart, granadilla, guanandi, gum, hackberry, hickory, hornbeam,hophornbeam, iroko, ironwood, kingwood, lacewood, limba, locust,mahagony, maple, marblewood, marri, meranti, merbau, oak, okoume, olive,pink ivory, poplar, purpleheart, ramin, redheart, sweetgum, sandalwood,sapele, sassafras, silky oak, silver wattle, sourwood, tamboti, teak,rosewood, tupelo, turpentine, walnut, wenge, willow, and zingana amongothers.

Utility

The above described compositions and methods find use in any applicationwhere an applied stimulus (e.g., temperature change) indicator isdesired.

In some embodiments, the subject compositions find use for a wide rangeof temperature, sensing, indicating, measurement, marking,cold-chain-management, perishable composition monitoring, safety,sensitizing, industrial, food service, pharmaceutical, industrial,processing, food processing, consumer products, household products, toyproducts, publishing, advertising, promotional dental, security,pharmaceutical, food products, novel packaging, skin care and skinhealth, pressure monitoring, temperature monitoring, humiditymonitoring, time monitoring, environmental monitoring, inventorymonitoring, medical and other market and/or product applications and thelike.

Compositions of the invention find use in early stage production,manufacturing, or synthesis stages through to end-of-use indicationwhere a product being monitored using an indicator or composition hasalready expired and is no longer of any further value. Compositions ofthe invention also find use in a variety of different applications,including but not limited to: color development for cold chainmanagement; ascending temperature indicator as color is develops;ascending temperature indicator where color development lock occurs atset points; shunted color development dependent on time along one axisand temperature along another; site addressable flash imaging usingascending temperature leuco dyes; 3D flash imaging using ascendingtemperature leuco dye; messages that appear as color develops ratherthan ink opacity changing to make message appear; reversible colordevelopment candles; reversible color development printable dyes;irreversible color development thermal inks and papers; toysapplications that turn color upon touching; ascending temperatureindicating composition for lotions and emollients; physiologictemperature status determination devices; hydration indicatingcomposition for lotions and emollients to determine physiologichydrations status; developers that co-act as alternative active agentse.g. flavors, fragrances, stimulants; long-term hysteresis effect andreversal using water reactivation based on aqueous slurry inks;long-term hysteresis effect and reversal using heat reactivation basedon aqueous slurry inks; flexographic in-line layering/manufacturing as aproduction means for tunable color indicating systems; ultra-sharpcritical melting point mediums for digital color development; ascendingreversible color development leuco dye; ascending reversible colordevelopment leuco dye with hysteresis; temperature adjustable ascendingcolor development leuco dye; micro-encapsulated ascending colordevelopment leuco dye; co-solvent-developer single component molecule;hydrochromic reversible color development leuco dye; mixed ascending anddescending reversible leuco dyes; natural co-developer-solvent forascending color development; natural co-developer-solvent for descendingcolor development; single component as dual solvent and color developerproperties; slurry concentrates of natural ascending and descendingleuco dyes; leuco dye color formers—developed by polydiacetylenicdevelopers; reversible color to colorless based on temperature;reversible colorless to color based on temperature; reversible color tocolorless based on hydration; reversible colorless to color based onhydration; reversible color to colorless based on solvation; reversiblecolorless to color based on solvation; irreversible colorless to colorbased on temperature; irreversible color to colorless based onsolvation; reversible non-hysteresis color change; reversible colorchange with hysteresis types; irreversible non-hysteresis color change;irreversible color change with hysteresis types.

Compositions of the invention also find use in low temperature rangemonitoring. Low temperature (−200° C. to 25° C.) application rangesinclude ranges for perishable items such as food, beverages, alcoholicbeverages, pharmaceutical products, blood, bio-pharmaceutical products,sensitive chemistries, rare materials, biological specimens, virulentbacteria and virus, DNA and RNA storage, and a number of othertemperature sensitive items or products that require temperature historyand storage conditions to be monitored and recorded.

Compositions of the invention also find use in medium temperature rangemonitoring. Medium temperature (26° C. to 60° C.) applications includeranges for perishable items that expire at elevated temperatures, warmholding temperatures, monitoring medium temperature processes forprocess validation and quality control, storage conditions, warmingfoods, monitoring plant growth conditions, monitoring environmentalconditions and living conditions, industrial applications includingmanufacturing processes, storage of explosives, monitoring shippingstorage containers from overseas suppliers, monitoring logistics offoods and goods cross country, in-flight monitoring of air freightedgoods, and the like.

Compositions of the invention also find use in high temperature rangemonitoring. High temperature (61° C. to 600° C.) applications includeranges for perishable items that expire at elevated temperatures, hotholding temperatures, monitoring hot temperature processes for processvalidation and quality control, storage conditions, heated foods,monitoring high temperature conditions, hot holding food serviceapplications where time and temperature monitoring is important, monitorfood processes that require limited time exposure at elevatedtemperature for food preparation, re-heating applications, microwavecooking applications where foods need to be heated and maintained atelevated temperatures for complete and thorough cooking, monitoringenvironmental conditions and living conditions, industrial applicationsincluding manufacturing processes, storage of military items, hightemperature monitoring shipping storage containers from overseassuppliers, novel autoclave and sterilization conditions, medicalequipment sterilization, monitoring logistics of foods and goods crosscountry, in-flight monitoring of air freighted goods, and the like.

Applications of Color Change Compositions

The following practical examples of applications for the subject colorchange compositions are offered by way of illustration and not by way oflimitation.

Substrate Types Utilized for Coating with Tunable Compositions:

The subject color change compositions can be applied and utilized with awide range of substrates (indicating substrates). Indicating substratecompositions include but are not limited to paper, plastic, hardsurfaces, soft surfaces, stiff or rigid surfaces, compliant surfaces,printed surfaces, printable surfaces, transparent surfaces,semi-transparent surfaces, opaque surfaces, non-transparent surfaces,skin, finger nails, molded surfaces, flexo-graphic printing surfaces,foam surfaces, expanded plastic surfaces, insulating surfaces,conducting surfaces, conducting ink surfaces, and the like. A substratecomposition can be comprised of thick or thin materials ranging inthickness from 1 nanometer to 100 centimeters. Often thicknesses willrange from 10 nanometers to 10 centimeters. More often substratessuitable for indicating compositions will range from 1 micron to 1centimeter. Typical substrates will range from 10 microns to 5millimeters and most often in the range between 0.1 millimeters and 1.0millimeters.

Optical Pattern and/or Message Development:

Optical patterns can be developed under triggering conditions usingoptical color change dye systems in combination with modeled substratesurfaces. An image can be generated by applying a pressure indicatingfilm over a substrate layer that has been pre-surface textured orpatterned. As temperatures are induced the dye layer initially comes incontact with the close proximity regions or features of the patternedsubstrate surface. An initial color change will occur in the dye layerthe emulates the upper surfaces of the substrate. As temperaturescontinue to increase, the dye layer may be forced in contact with lowerregions of the substrate surface texture. Images or patterns can appeardifferentially as a result of the final temperature induced between thetemperature indicating dye layer and the patterned or texturedsubstrate. Partial images can be made to occur at lower temperatures.More complete or developed images or messages can be made to appear atmedium pressures. Fully developed images or completed messages can bemade to appear at final desired induced temperature.

Machine-Readable Chemistries and Device Configurations:

In certain embodiments, the subject compositions of the invention finduse in machine-readable applications. Machine-readable chemistry anddevice configurations can include, but are not limited to, variousprinted barcodes, Interactive barcodes, abuse security barcodes; 1D, 2D,and 3D; barcodes holographic barcodes, vision imaging systems, transientbarcodes, time-only barcodes, freshness indicating barcodes, shapememory bar codes, and a variety of other applications and formats.

Compositions herein can be formulated and utilized in a variety ofvisual, scanning, imaging, and machine readable processes as they relateto temperature monitoring algorithms. Messages or codes can be made toappear or disappear; parts or elements of graphics, symbols or codes canbe utilized to make the element, graphic, or code un-discernable orunrecognizable until that portion of the medium has changed withtemperature or the like.

Color change compositions can be utilized in both visual and machineaided formats. Visual readings are made with distinct visualdetermination of a threshold color change that occurs. Machine aidedformats are made using an optical or electrical interpreted change in acolor hue or conductive characteristic in a co-topo-polymericcomposition that undergoes a state threshold change. By way of example,but not limitation, a composition can be printed or formulated in amachine viewable format. A measurable reading may be taken of an initialcolorimetric state. A second or sequential reading can be measured asthreshold state occurs. During the transition from one state to anotherstate, an instrumented reading can be registered. The thresholdtransition can be measured against a calibrated reading such that thedegree or magnitude of the state threshold change can be recorded andmonitored. Recorded and monitored machine measurements can be displayedby instrumentation utilized in the machine aided format.

Machine readable/responsive barcodes can be utilized for determining thepresence of or responding to a temperature fluctuation, visible light,ultra-violet light, irradiation for applications such as foodsterilization including gamma and cobalt 60 irradiation levels,hydration, pressure changes, high pressure events including highpressure sterilization, contaminations such a heavy metal contamination,alcohol levels, poisons, chemical sensing, biological compositions,chemical reagents, non-specific analyte binding, specific analytebinding, gases, physical and mechanical responses, UV intensity, lightintensity, sanitization conditions, mechanical stress conditions,pressurization formats, oxidation state, optical bleaching, end-of-useindication, time, time and temperature, free radical content, hydrationstate, skin care health, medical sterilization, clinical health status,indicating sensors on food storage containers medical status, securityapplications, anti-tampering applications, and any of a number of othermeasurable indicia.

Machine readable codes for indicating time duration for productshelf-life and use indication can be accomplished using sensingcompositions that shift spectrally in response to ambient conditions andproduct storage.

Also of interest are barcodes embedded or obscured with the subjectcolor change composition that is selectively revealed upon triggering atset points of co-topo-polymeric indicator.

A range of barcode languages can be utilized that can be partially offully associated with a composition and therefore act as a machinereadable indication means to measure and report the selectivefunctionality intended to comprise the co-topo-polymeric compositionused for indication. Barcode types include, but are not limited to anylanguage, a wide range in size and numbers of character, as well as thebarcode language of interest: 39, 93, 128A, 128B, 128C,

A standard barcode or UPC code can be obscured, coated, embedded in orover-laid by a mixed or single component chromic change agent. Part ofthe standard bar code can be clearly visible at the beginning of readingso as to generate an initial starting parameter set. Selective portionsof the barcode can be covered by discrete compositions that are set tochange color at pre-determined temperature exposures. As the barcode isplaced on a product type at a lowered temperature the chromic changeagent can be activated. On activation, pre-determined elements of thecode will be obscured by the optical density of the chromic change agent(i.e., the color change composition). The optical density of the barcodewill be set such that a barcode reader will not be able register theobscured portion/bars that represent a specific code sequence. As thebarcode/product is raised in temperature and as pre-selected temperatureare achieved and exposed, a pre-determined section of bar code will berevealed (reversibly or irreversibly depending on the nature of thechromic change agent selected). As each temperature threshold isachieved during the temperature exposure process, eachpre-determined/coated barcode region will be come machine readable. Insome instances, an indicator may be configured as a linear segmentedbarcodes that differentially respond to temperature and/ortime-temperature along their axis.

Non-readable or partially readable barcodes utilizing single or mixedcompositions as the obscuring agent are readily scanned for activity orinactivity in part or in whole.

Compositions herein and other blue/black bar codes provide a uniqueoptical masking characteristic that makes a partially readable of fullynon-readable part or all of the modified bar code. In addition thetransition of a blue/black compositions and compounds to a red or orangehue including but not limited to light pink to dark red hues, providesfor high optical readability by most commercial barcode readers sincethe red, orange, pink or related hues are optically transparent to thered light sources utilized in standard barcode readers.

Readable barcode languages include but are not limited to: Morovia Code25, 11, 12B. 139. UPC-A, UPC-E, EAN-8, EAN-13, code 128b, USS 39, USD 3,3 of 9 code, code 39. hibcc. Java applet, logmars, full, symbology,industry 2 of 5, discrete, self checking codes, msi, plesssey,one-dimensional barcodes, two-dimensional barcodes, three-dimensionalbarcodes, halographic barcodes, luminescent barcodes, and the like.

Barcode formats of interest include, but are not limited to: Off to Onswitching barcodes; On to off switching barcodes; Codes 39 and 93 forembedded thermal messaging; various barcode geometries, such as planar,curved, round, etc.; barcodes configured for thermal delay for timetemperature coding; freshness indicating barcodes; time-only indicatingbarcode; etc.

In some instances, one may have re-programmable barcodes that can bere-set among, in between or adjacent to a bar code set throughre-printing a region of interest.

Activation Label for Monitoring Time-Temperature Color Development:

Activation or initiation of the time and temperature dependent colordevelopment process begins upon intimate interaction of essential systemcomponents. Activation can be accomplished manually by applying a labelcontaining one component to a substrate containing a second member. Bothmembers are required for initiation and color development. In a secondexample activation can begin upon label application and contact betweentwo members of the full color development pair by using automatedlabeling equipment.

Wrap around label applicators can be used for activation at the labelingpoint using labels constructed with one member of a color system on onesurface and the other member on the opposing surface. During wrap aroundlabel application the bottom portion of a label will come in contactwith the second member to initiate the color development process.

Pull tab activation finds use where semi-manual activation approachesare desired. A pull tab can be used to separate the two component colordevelopment system such that when the separation tab is pulled, thepulling process draws one layer member in intimate contact with theother layer member. Activation begins during the adhesion process.

Blocking layers can be utilized where by the blocking layer keepsdormant and maintains separation between two layer components until anelevated temperature or time is achieve. When a threshold temperature isachieved thereby melting or diffusing the blocking layer, both colorformer and color developer layer are allowed to interact and the colordevelopment process can proceed above the designated temperature or atany point where the blocking layer is eliminated.

Pressure initiated activation can be utilized whereby pressure isrequired to force on layer of a pair in direct contact with the secondlayer to induce intimate contact. Off-setting spacers can be used toseparate one layer from the other. A gap can be placed between the twolayers filled by only air or a displacing composition. As presser isplaced on one layer, the second layer is forced to interact and initiatethe color development process.

Blister packing constructs can be utilized where by on member of anactivating pair can be placed distal to a second layer using adisplacing plastic indented structure. As the indented structure isdeformed or flattened, the deformation process forces both members ofthe color development pair to interact and initiate the colordevelopment process.

Bubble burst activation can be utilized whereby both members of a colordevelopment pair are separated by an air or gas pocket. Separation isdisrupted by pressing and rupturing the bubble. An added sound effectcan be elicited as an audio confirmation of initiating the colordevelopment process. Bubble separators can be further used to generatepatterns during multiple adjacent ruptures. Advertising or promotionalapplications will find use as arrays of bubble activating patterns canbe utilized.

Direct Thermal Label and Color Sensitive Medium Integration:

Completed constructs can be utilized where existing thermal papers,films, labels or substrates and carbonless papers, films, or substratescan be paired with the subject color change compositions. An examplecarbonless copy paper may be prepared by placing a first sheet of papercoated on one side with a hydrophilic colloid solution in which aredispersed microcapsules of oil droplets containing a colorless electrondonor dye into contact with a second sheet of paper coated with anabsorbent and an electron accepting color developer compound. The heatresistance and moisture resistance of the copy paper is substantiallyimproved by adding to the hydrophilic colloid solution a graft copolymerhaving a backbone of carboxymethyl cellulose or gum arabic and sidechains of polyacrylic acid or polymethacrylic acid. The image responsetime of the second sheet can be improved by adding pectin or sulfatedstarch to the coating. Substrates such as these can be utilized incombination with the subject color change compositions create a time ortime-temperature indicator device.

Time-Temperature and Temperature Thermometers:

Visually read thermometers and sensors can be produced using the subjectcolor change compositions. Thermometers can include a color forminglayer on a substrate, a delay or temperature responsive blocking layer,and a pre-adhered color developing layer. The selection of componentscan be used to pre-set the time-temperature and temperature triggeringtemperature threshold of the thermometer.

In particular, the blocking layer positioned between the color forminglayer and the adhered color developing layer can be formulated with ablocking compound that responds to and transforms to a permeable layerat a specified temperature. For example, the blocking layer may be asharp melting point medium such as a wax, paraffin, or othercommercially available sharp melting point medium. Upon melting,softening, or becoming permeable, the blocking layer will no longer beable to block or inhibit interaction between the color developmentsystem and an irreversible color will develop at the pre-determinedtemperature setting.

A time-delay can be introduced into the thermometer by adjusting thediffusion path, permeability characteristics of the blocking layer,composition of the color forming layer, and composition of the colordeveloping layer, such as for example 1 second or more, such as 5seconds or more, such as 60 seconds or more, such as 5 minutes or more,such as 30 minutes or more, such as 1 hour or more, such as 5 hours ormore, such as 10 hours or more and including 24 hours or more.

Thermometers employing the subject compositions can measure temperaturesranging from sub-freezing to over 1,000° C. In some embodiments, thetemperature ranges from −5° C. to 500° C., such as from 10° C. to 250°C.

Graphics and Messaging:

Messages, symbols, illustrations, titles, graphics, text, text messages,messages in general, images, icons, licensed figures, numerical values,hidden messages, line art, detailed art, multi-colored images, embeddedgraphics, graphic elements or entire graphics, visual que's, obscuredimages, partial images, pricing information, security information,promotional information, safety information, marks, patterns, and thelike can be combined with the subject color change compositions.

Graphic and messaging information can be printed with the subject colorchange compositions and combined with stationary graphics and messages.In addition, stationary inks and the subject color change compositionscan be combined in ways to generate messages that appear and disappear.

Graphic overlay patterns can be employed whereby the graphic overlayobscures an a color developing graphic or message composed of thesubject color change composition. As the color change compositionundergoes chromic transition, the color obscured by the stationarygraphic overlay pattern until development proceeds to an intensity thatthe developing ink becomes discernable through the graphic overlaypattern.

Alternatively, a developing graphic or image comprising the developingink can be printed in a trapped pattern that is compatible or continuouswith the developing ink. Initially, the message is apparent. As thedeveloping ink continues to develop, it will become similar in pattern,hue, and intensity with the stationary graphic. At a pre-described timeor time-temperature profile, the developing pattern color and patternmatches the stationary pattern and becomes indiscernible against thebackground and the message or graphic appears to disappear.

A wide range of graphic and messaging formats can be utilized toemphasize, obscure, confuse, re-register, change, morph, transition,alter, become apparent, alter, integrate or the like to achieve adesired result that best suit the readout or resulting effect intendedfor a particular product application of interest.

The following examples are offered by way of illustration and not by wayof limitation.

Experimental Color Former/Color Developer Compositions A. ReversibleColor Development Hydrochromic Inks:

A pre-colored reversible hydrochromic ink is prepared using a twocomponent solution mixture containing developer and color former. Thedeveloper solution is prepared using 10% by weight developer (Pergafast201, Ciba AG CH) dissolved in 90% polyethylene glycol average molecularweight 1,450 g/mol (Sigma Chemicals). The mixture is brought above 200°F. and mixed until the solution becomes clear. A color former solutionis prepared using 20% by weight color developer Specialty Magent 20(Emerald Hilton Davis, LLC) dissolved in 80% by weight polyethyleneglycol average molecular weight 1,450 g/mol (Sigma Chemicals). Themixture is brought above 200° F. and mixed until the solution becomesclear.

The developer solution and color former solutions are kept heated mixed.A slight magenta color develops. The solution is allowed to cool to 160°F. 3 volumes of hot water (greater than 160° F.) is added duringvigorous mixing. An immediate magenta colored emulsion is formed and thesolution is allowed to thicken during cooling to room temperature. Tothe concentrated slurry, one or more of acetate polymer ethyl vinylacetate or acrylate polymers ethylene ethyl acrylate, ethylene methylacrylate or ethylene butyl acrylate may be added. The concentratedslurry having incorporated copolymer may be removed for addition to anink vehicle or used directly as a coating ink.

B. Reversible Color Development Hydrochromic Papers:

An aqueous slurry ink is coated on standard white bond paper. Thecoating is warm air dried. The initially colored—hydrated ink isconverted to a colorless state during drying. Drying and conversion to acolorless state may be facilitated using forced warm air.

Color markings, drawings, graphics, message writing, symbols and thelike may be generated by applying a water marker, pen, swab, stamp tothe colorless coated area of the paper. Colors generated by contact withwater are observed to dissipate within minutes upon drying. The colordevelopment and color dissipation is reversible over a large number ofapplications.

C. Reversible Color Development Composition Based on AscendingTemperature:

A simplified and intense ascending reversible color development coatingcomposition is prepared using a single component phase separating colordeveloper and a single component color former. 83% by weight of colordeveloper glycerol monostearate (2,3-dihydroxypropyl C18, GMS) is heatedto 180° F. to ensure complete melting and low viscosity. 17% by weightgreen color former (Pergascript™ green I-2GN, Ciba AG CH) is added as apowder, mixed and heated (>180° F.) until completely dissolved. Thecolor former is observed to turn deep green as it dissolves to a richdark green mixture. The mixture retains a deep green color provided thatit remains molten. To the composition was added at one or more ofacetate polymer ethyl vinyl acetate or acrylate polymers ethylene ethylacrylate, ethylene methyl acrylate or ethylene butyl acrylate. Coolingto room temperature results in a transition of the formulation to anoff-white slightly tinted waxy solid.

D. Reversible Ascending Temperature Color Development Substrates:

A reversible ascending temperature color change substrate is preparedusing the reversible color development composition prepared in ExampleC. A solidified room temperature composition is heated to 160° F. untilit is deep green and molten. The molten composition is then applied topaper substrates by a variety of standard coating processes. Forconvenience, the composition is roller coated on a standard 80 poundbonded white paper. Rollers are pre-warmed to ensure even coating.

Uniform coatings are applied to paper substrates. The coatings coolrapidly at room temperature (68° F.). Initially colored coatings turnfrom a deep green coloration to a translucent off white color uponcooling. The coating penetrates well into the paper substrate providinggood stability on the paper. Cooled non-colored coatings are changedfrom colorless state to a colored state upon raising the temperatureabove the melting transition of the ascending color developer glycerolmonostearate. The color completely reverses upon cooling back to roomtemperature. The ascending color change is reversible over continuedrepeated cycles and long term storage.

E. Micro-Encapsulation of Reversible Color Development Compositions Baseon Ascending Temperature:

An ascending reversible color development coating composition isprepared using a single component phase separating color developer and asingle component color former is prepared in accordance to Example Cabove. 83% by weight of a ascending color developer glycerolmonostearate (2,3-dihydroxypropyl C18, GMS) is heated to 180° F. toensure complete melting and low viscosity. 17% by weight green colorformer (Pergascript™ green I-2GN, Ciba AG CH) is added as a powder,mixed and heated (>180° F.) until completely dissolved. The colordeveloper turns deep green as it dissolves to a rich dark green mixture.The mixture retains a deep green color provided that it remains molten.To the composition was added at one or more of acetate polymer ethylvinyl acetate or acrylate polymers ethylene ethyl acrylate, ethylenemethyl acrylate or ethylene butyl acrylate.

The mixture is homogenized and dispersed in an aqueous medium until theaverage particle size is 2 microns. The color former dispersion is thenadmixed by stirring first with a 70% strength by weight aqueous solutionof melamine-formaldehyde resin (molar ratio of melamine:formaldehyde1:6) and a 20% strength by weight aqueous solution ofpolyacrylamidomethylene-propanesulfonic acid in a weight ratio of 1:1and subsequently with a normalizing amount of sodiumdihydrogenphosphate. The mixture is then adjusted with formic acid to pH4.2. After mixing at room temperature for one hour and the addition of2.5 g of water, the mixture is stirred at 160° F. for 2 hours untilcuring was complete.

A micro-encapsulated slurry is obtained in approximately 30-40% byweight aqueous dispersion of ascending reversible color generatingreverse leuco dye which is colorless at room temperature and becomesreversibly intensely colored above the melting transition of theco-developer/solvent GMS.

The micro-encapsulated composition subsequently is either separated anddried to a powder form to be admixed to non-aqueous printing vehiclessuch as UV curable ink resins or solvent based in resins or is useddirectly as an additive to aqueous slurry to be added to aqueous basedprinting vehicles.

F. Separate Reversible Red, Blue, and Green (RGB) Color DevelopmentCompositions Based on Ascending Temperature for Color Image Development:

Color enriched ascending reversible color development coatingcompositions are prepared using a novel single component phaseseparating color developer and a single component color formers. 80% byweight of an ascending color developer glycerol monostearate(2,3-dihydroxypropyl C18, GMS) is heated to 180° F. to ensure completemelting and low viscosity. 20% by weight either red, blue, or greencolor formers (Pergascript™, Ciba AG CH) are added as powders, mixed andheated (>180° F.) until completely dissolved. The color formers turndeep independent colors as they each dissolve. The mixtures retain adeep red, blue or green color provided that they remain molten. Coolingto room temperature results in a transition of the formulation to anoff-white slightly tinted waxy solid.

Each RGB color development composition is utilized in a 3-color printingprocess to generate a realistic color image. The initial printingprocesses require careful plate positioning to ensure colorregistration. Color printing is accomplished while the color developmentcompositions are elevated in temperature and in the colored state. Uponcooling to room temperature, the image disappears on the paper printingsubstrate. As the substrate is warmed, the image appears from a blankpage reversibly until the page is cooled again back to room temperature.The reversible ascending temperature effect provides an unusual anunexpected image development process as compared to standard availableleuco dye compositions that can only be used to reveal an underlyingimage.

G. Separate Reversible Red, Blue, and Green (RGB) Color DevelopmentCompositions and Generation of Hydrochromic Full Color ImageDevelopment:

Color enriched hydrochromic reversible color development coatingcompositions are prepared using novel color former/developercompositions. Pre-colored RGB reversible hydrochromic inks are preparedusing independent two component solution mixtures containing developerand color former as described in Example I. The developer solutions areprepared using 10% by weight developer (Pergafast 201, Ciba AG CH)dissolved in 90% polyethylene glycol average molecular weight 1,450g/mol (Sigma Chemicals). Each mixture is brought above 200° F. and mixeduntil the solution becomes clear.

Separate color former solutions are prepared using 20% by weight colordeveloper Specialty Red, Specialty Blue, or Green (Emerald Hilton Davis,LLC) dissolved in 80% by weight polyethylene glycol average molecularweight 1,450 g/mol (Sigma Chemicals). The mixture is brought above 200°F. and mixed until the solution becomes clear.

Corresponding color developer solutions and color former solutions arekept heated mixed and kept independent. Slight colors are developed uponmixing. The solutions are allowed to cool to 160° F. 3 volumes of hotwater (greater than 160° F.) are added during vigorous mixing. Animmediate red, blue or green colored emulsion is formed and thesolutions are allowed to thicken during cooling to room temperature. Theconcentrated slurries can be removed for addition to an ink vehicle orused directly as a coating ink.

The aqueous slurry inks are printed in RGB patterns on standard whitebond paper. The coating is warm air dried. The initiallycolored—hydrated ink is converted to a colorless state during drying.Drying and conversion to a colorless state are facilitated using forcedwarm air.

Full color images, multi-colored markings, drawings, graphics, messageswriting, symbols and the like can be generated by applying a watermarker, pen, swab, or stamp to the colorless coated area of the paper.Colors generated by contact with water are observed to dissipate withinminutes upon drying. Color image development and color dissipation arereversible over a large number of applications.

H. Coacervation Micro-Encapsulation of Reversible Color DevelopmentCompositions for Ascending Temperature Color Change Dyes:

150 ml 8% aqueous solution of 200 Bloom Type A Gelatin at 50° C. iscombined together with 0.1 ml of n-octanol as a foam suppressant. 80 gmof 2,3-glycerol monostearate is pre-mixed with 20 gram color formerPergascript™ orange I-G (Ciba AG CH) and then mixed into the aqueoussolution with agitation to form oil phase droplets in the range of 10-20microns. The emulsion pH is adjusted to pH 5. 10 ml of a 28% solution ofsodium polyaspartate diluted with an additional 40 ml of water is addedto the emulsion during mixing. An additional 170 ml of distilled wateris subsequently added. The pH of the mixture is then lowered to 4.4 byaddition of glacial acetic acid. The mixture is cooled to about 10° C.and the pH lowered to pH 4.2. The solution is allowed to cool 45 minutesat 10° C. whereby 5 ml of a 25% glutaraldehyde solution is added and themixture allowed to stay 12 hour at 22° C.

The micro-encapsulated composition is subsequently either separated anddried to a powder form to be admixed to non-aqueous printing vehiclessuch as UV curable ink resins or solvent based in resins or is useddirectly as an additive to aqueous slurry to be added to aqueous basedprinting vehicles.

I. Natural Co-Developer-Solvent Based Leuco Dye Compositions:

A natural co-developer-solvent leuco dye is prepared by pre-melting 80%camauba wax to 100° C. Color former is added at 20% by weight and mixed.The mixture is heated and mixed until the color developer is completelydissolved into a clear molten solution. The molten solution is allowedto cool to room temperature. Upon cooling the composition is solidifiedto a rich deep color. The solidified colored composition exhibited fullyreversible color change characteristics upon heating and melting andchilling and solidification. The solidified composition could be useddirectly as a coating or converted to a powdered form for addition toprinting vehicles, plastics extrusion compositions, injection moldingcompositions or the like.

J. Aqueous Coating and Product Additive Slurries Using NaturalCo-Developer-Solvent Based Leuco Dye Compositions:

Aqueous slurries of natural co-developer-solvent based leuco dyecompositions prepared as described in Example I above are emulsifiedusing food-grade surfactants and ultra-sonication. A 20% by weightemulsifier solution of Protanal Ester BV 3750 (FMC Biopolymer) isprepared by adding and mixing the surfactant in stirring water at 70° C.until the emulsifier is completely dissolved. 50% by weight naturalco-developer-solvent based leuco dye compositions are heated to aliquefied state (100° C.). 50% by weight pre-heated emulsifier solutionis added and the mixture is sonicated using a 300 watt ultrasonicatorprobe. A uniform slurry emulsion is formed within 2 minutes ofsonication. The slurry is allowed to cool to room temperature. Theslurry may be used directly as a coating ink or utilized at variousconcentrations as an additive to ink vehicles. Pre-formed slurries canbe further micro-encapsulated using standardized micro-encapsulationprocesses describe above.

K. Leuco Dye/Polydiacetylenic Combinatorial Compositions in whichDiacetylenic Moieties Serve as Color Developers and Possess IntrinsicColor Change Polymer Characteristics:

10% by weight color formers—either red, blue, or green (Pergascript™,Ciba AG CH) and 10% by weight 10,12-tricosadiynoic acid (C23) aredissolved is dichloromethane. The presence of the free monomeric C23acid initiates color development in solution. The solutions are tintedrelative to the color type. Each formulation is dried on to paper. Theresulting colors are rich in hue. Each color type exhibits a reversiblecolor change when elevated above 160° F.

Dried color draw-downs are subsequently exposed to UV light (254 nm)resulting in the formation of an additional blue hue to each color typeexposed. The blue hue s generated by the topochemical polymerizationreaction forming the ene-yne polydiacetylenic polymer backbone. The bluehue may be irreversibly changed to a red hue during heating or throughfrictionally induced mechanochromic triggering. The leuco dye reversiblecolor change is convoluted with the polydiacetylenic color transition.

L. Solvent Based Compositions for Inkjet, Drop-on-Demand, and ContinuousInkjet Printing:

10-15% by weight color formers and developers are dissolved in solventsystems including ratios of chloroform, methylethyl ketone, and alcoholtypes. Soluble resins such as polyethylene glycol and other soluble, butadherent polymers may be used. Soluble solutions are used directly asprinting ink compositions in various inkjet, drop-on-demand, andcontinuous inkjet printing formats.

M. Plastic-Wood Pseudo Master Batch:

Wood flour is finely pulverized wood that has a consistency fairly equalto sand or sawdust, but can vary considerably, with particles ranging insize from a fine powder to roughly the size of a grain of rice. Mostwood flour manufacturers are able to create batches of wood flour thathave the same consistency throughout. All high quality wood flour ismade from hardwoods because of its durability and strength. Verylow-grade wood flour is occasionally made from sapless softwoods such aspine or fir. Wood flour is commonly used as a filler in thermosettingresins such as bakelite, and in linoleum floor coverings. Wood flour isalso the main ingredient in wood/plastic composite building productssuch as decks and roofs. Prior to 1920, wood flour was used as thefiller in thick Edison Diamond Discs.

Wood flour has found a use in plugging small through-wall holes inleaking main condenser (heat exchanger) tubes at electrical powergenerating stations via injecting small quantities of the wood flourinto the cooling water supply lines. Some of the injected wood flourclogs the small holes while the remainder exits the station in arelatively environmentally benign fashion. Large quantities of woodflour are frequently to be found in the waste from woodworking andfurniture companies. An adaptive reuse to which this material can bedirected is composting.

Emulsifying wood powder-flour with plasticizing emulsifiers and incombination, emulsifying and dispersing powderized plastics and dyesprovides for an several advantages of create new plastic-wood productbased on pseudo master batch formulations. Intrinsically, wood is ahydrophilic composition as compared to plastic primarily beinghydrophobic in composition. Pseudo master batch formulations andprocesses provide an enabling method to enhance plastic wood dispersion,alter the individual characteristics of each component, provide for theuse of recycled wood products and plastic products, reduces the stepsrequired for materials processing compared to conventional methods ofcombining wood and plastic compositions, dramatically improve theenvironmental impact producing plastic-wood products compared toconventional processing techniques, and improve manufacturingefficiencies and therefore reduce overall cost and pricing to consumers.

Pseudo master batch plastic-wood can be compounded utilizing either dryor pre-dampened wood powder/flour mixed at specified rations with apre-powderized granulated plastic composition. The mixture ishomogenized and treated in a single-continuous mixing step with a liquidplasticizing emulsifier and any desired ancillary dye or treatment agent(e.g. lubricating agent, preservative, UV inhibitor, anti-caking agent,slip agent, or the like). The compounded and mixed composition can bedried by any of a variety of means to a level of less than 1% water andmade ready for extrusion to plasticized pellets, directly utilized forplastics processing or stored for later use.

Upon compounding and drying, pseudo master batch plastic-wood can beeither further palletized by extrusion in to resin based pellets andused or sold for industrial processing into products or used directly ina powderized form in extrusion or injection molding. By way of example,wood-plastic coffee stir stick can be extruded into forms, sizes andshapes consistent with standard wooden coffee stir sticks. The color canbe adjusted to create a wood-like look. A texture can be embossed togive the stick a wood-like appearance and feel. Wood-plastic productsproduced from pseudo master batch processes have significant market andproduct advantages including but not limited to: ecological benefits inthat both recycled wood and plastic can be utilized; the wood componentin the end product will improve bio-degradation compared to plasticalone in landfills; further environmental benefits since lessdeforestation and petroleum utilization are desirable; cost benefitsover virgin plastic or wood products in that fully recycled plastic andwood can be utilized; sterilization due to the high temperatureprocessing utilized; and rapid and efficient production to furtherreduced costing and ultimate consumer pricing.

N. Lab Scale Thermochromic Micro-Encapsulation Using InterfacialPolymerization:

Materials:

Materials for Micro-Encapsulation:

-   -   Distilled water (dH2O)    -   Sigma Aldrich Poly(methyl vinyl ether-alt-maleic anhydride        copolymer) [MVEMAC], item #416339, CAS #9011-16-9    -   Sigma Aldrich 1-Tetradecanol and 1-Hexadecanol (or other oil        phase medium)    -   Sigma Aldrich Bisphenol AP (4,4′-(1-Phenylethylidene)bisphenol.        Item #450456, CAS #1571-75-1    -   Color Formers Blue 5, Green 2 and Red    -   Sigma Aldrich Poly(melamine-co-formaldehyde), methylated, 84 wt        % solution in 1-butanol, item #418560    -   5% Sodium Hydroxide solution in dH2O [EMD Chemicals Sodium        Hydroxide, item #SX0593-1, CAS #1310-73-2]    -   5% Acetic Acid solution in dH2O [EMD Chemicals Acetic Acid,        Glacial, item #AX0073-6, CAS #64-19-7]    -   Warm dH2O, heated in microwave or oil bath    -   Hot oil bath filled with Crystal Plus Mineral Oil T500    -   125 mL Erlenmeyer glass flask with magnetic stir bar inside    -   Hot air gun and vortex    -   2 small scintillation vials    -   30 mL glass vial, VWR item #VW60910A-8    -   Omni GLH-115 Homogenizer and 10 mm rotor stator probe    -   Parafilm, spatula or wooden coffee sticks, disposable 1 mL        plastic pipets

Procedure:

-   -   1. At least two hours before starting microencapsulation,        prepare a 5% solution of MVEMA in dH2O. In the 125 mL Erlenmeyer        flask, add 5 g of MVEMAC to 95 mL of dH2O. Cover the end with        parafilm and heat the flask in the oil bath at 60° C. for at        least two hours, or until solution becomes completely        transparent, though a slight yellowish hue is fine. Store        solution in refrigerator when not in use.    -   2. Preheat the oil bath to 85° C. with a stir speed of 300.    -   3. Measure 10.4 g of 5% MVEMAC into a 30 ml vial and place into        the oil bath at an angle. Allow the solution to equilibrate,        about 30 minutes. Leave the cap on loosely so the water in the        solution does not evaporate out.    -   4. In a small scintillation vial, add 3.4 g of oil phase        (1-Tetradecanol), 0.96 g of color developer (Bisphenol AP), and        0.48 g of color former (Blue 5). Heat with the hot air gun and        vortex until color former is dissolved and solution is        transparent. Add solution to the 30 ml vial. Do not overheat the        solution or else the dye will burn causing discoloration in the        final capsules.    -   5. Tape the hole near the top of the 10 mm probe closed. Screw        in the 10 mm probe and insert it towards the bottom of the vial        and run the homogenizer at speed 1. Move the homogenizer up and        down a few times to ensure homogenous mixing. After a minute,        increase the speed to 2, then after another minute up to speed        3.    -   6. Add 1 mL (˜32 drops) of 5% NaOH dropwise into the vial,        moving the homogenizer up and down to mix. Run reaction for 15        minutes.    -   7. Half-fill a scintillation vial with melamine formaldehyde.        Using the hot air gun, heat the vial containing melamine        formaldehyde until it is liquid (˜1 min). Move the probe to the        side and add 1 mL of melamine formaldehyde. Move probe up and        down to ensure proper mixing. After a minute, repeat the process        four more times until 5 mL (˜2.8 g) of melamine formaldehyde is        added. Do not add too quickly or else the slurry will coagulate        and thicken unevenly. Run reaction for another 15 minutes.    -   8. Gradually add 1 mL (˜32 drops) of 5% acetic acid dropwise,        four drops at a time, moving the probe up and down. Reduce the        rotor stator speed to 2.6 (two clicks). Run the reaction for 15        minutes then add another 1 mL of acetic acid dropwise, eight        drops at a time, moving the probe up and down. Reduce the rotor        stator speed to 2 (three more clicks). Run the reaction for        another 15 minutes. Shut off homogenizer.

While running the reaction, use an applicator stick to place a sampleonto a piece of paper at the following intervals: after adding NaOH,after adding melamine formaldehyde, after each addition of acetic acid,and at the end. Use the hot air gun to test color fading. Record resultsin notebook.

O. Thermochromic Pseudo Master Batch Scale Up Using Single PolyethyleneResin

For industrial scale processing, 24 kg pseudo master batch wet powderwas prepared using 30% by weight aqueous thermochromic slurry (19° C.blue, BPA-free at 50% by weight micro-encapsulated pigment, SeganIndustries, Inc. CA), 10% by weight aqueous liquid surfactant (MichelmanCorp. ME09730-FD), and 60% by weight powered/pulverized polyethylene(ROTO PE 625662, Ashland Distribution). One example sequence of additionincludes pre-coating the powdered polyethylene carrier resin bycontinuously mixing it in an agitation mixer, adding the liquid emulsionand then continuing to mix until the polyethylene powder is uniformlywetted by the emulsion (10 minutes). The thermochromic slurry is thenadded consistently to the mixing composition and the mixing is continueduntil the composition is thoroughly mixed and homogenized (10 minutes).

Once mixing is complete, the wet theromochromic pseudo master batch isthen dried to a uniform granular flowing powder. Upon drying, the driedpseudo master batch can be further compounded prior to utilization orprocessing by the addition of lubricants such as ethylenebis(stearamide) and color stabilizers described in this case such asethyl vinyl acetate. Typically ethylene bis(stearamide) (EBS), is addedat 3-4% of the powdered pseudo master batch used and ethyl vinyl acetateis added at 15% of the powdered pseudo master batch used.

Each component was added to a mixing vessel and mixed thoroughly to auniform paste. The paste was flash spray dried in a drum dryer at belowthe melting transition of the PE (210° F.) and collected as a largegranulated composition (0.1 inch diameter average particle size). Driedpseudo master batch could be used directly for PE or PP extrusion orinjection molding applications between 2% to 10% by weight in themolding resin. Molded articles prepared with pseudo master batch showedgood color uniformity and thermochromic color change activity at theintended temperature for use.

P. Thermochromic Pseudo Master Batch Scale Up Using Dual PolyethyleneResin

For industrial scale processing, 24 kg pseudo master batch wet powderwas prepared using 30% by weight aqueous thermochromic slurry (30° C.blue, BPA-free at 50% by weight micro-encapsulated pigment, SeganIndustries, Inc. CA), 10% by weight aqueous liquid surfactant (MichelmanCorp. ME09730-FD), and 30% by weight powered/pulverized polyethylene(ICO Polymers, LLP 8555.25) and 30% by weight additional polyethylene(BAPOL, LLDPE 2272G). One example sequence of addition includespre-coating the powdered polyethylene carrier resin by continuouslymixing it in an agitation mixer, adding the liquid emulsion and thencontinuing to mix until the polyethylene powder is uniformly wetted bythe emulsion (10 minutes). The thermochromic slurry is then addedconsistently to the mixing composition and the mixing is continued untilthe composition is thoroughly mixed and homogenized (10 minutes).

Once mixing is complete, the wet theromochromic pseudo master batch isthen dried to a uniform granular flowing powder. Upon drying, the driedpseudo master batch can be further compounded prior to utilization orprocessing by the addition of lubricants such as ethylenebis(stearamide) and color stabilizers described in this case such asethyl vinyl acetate. Typically ethylene bis(stearamide) (EBS), is addedat 3-4% of the powdered pseudo master batch used and ethyl vinyl acetateis added at 15% of the powdered pseudo master batch used.

Each component was added to a mixing vessel and mixed thoroughly to auniform paste. The paste was dried in laminar forces air drier system at120° F. for 2 hours and collected as a large granulated composition (0.1inch diameter average particle size). Dried pseudo master batch could beused directly for PE or PP extrusion or injection molding applicationsbetween 2% to 10% by weight in the molding resin. Alternatively, theresulting pseudo master batch could be palletized using an extrusionpalletizing unit with zone temperatures of 80° C. for 6 temperaturezones, 85° C. for zone 7, a materials handling zone at 120° C., and adie extrusion zone at 120° C. Pellets were cleaved, cooled, and driedusing a front face water ring pelletinzing system. Final pellets couldbe used in injection molding and extrusion from between 3% to 10% byweight.

Q. Evanescent Micro-Encapsulation Formulation

Prepare for the micro-encapsulation by heating up 20.8 g of thepreviously prepared solution of 10% Poly Methyl Vinyl Ether-Alt-MaleicAnhydride in de-ionized H2O (MVEMA) in an oil bath to 75*C for 30minutes. Also, measure out 12 mL of melamine formaldehyde into a spicejar and leave it in the oil bath, until ready to be use. During thattime, ensure that the rotorstator used to emulsify the microencapsulatedsolution is sufficiently cleaned and ready to use. The rotorstatorblends the micro-encapsulation solution into a consistent slurry, makingit easier for the encapsulations to form. Throughout the experiment,move the rotorstator around the spice jar to ensure completemicro-encapsulation of the whole solution within.

In an amber, UV protected vial, put 6.8 g of oil phase medium and 0.12 gof D&C dye. The lower the melting point of the oil phase medium, theeasier the micro-encapsulation process will progress and the moresignificant the evanescent will be. The purpose of this experiment is toachieve an encapsulation where the D&C dyes are encased in the capsuleso that they do not stain, but still evanesces when exposed to light.

Further reactions are performed in a dark room using red lighting,adequately protected from all potential UV light, for the duration ofthe experiment and take measures to prevent exposure to light. Heat upthe oil phase medium and dye mixture with a hot air gun until the oilphase medium has melted completely and mixed together with the dye. Waituntil the mixture has solidified, then add 1.2 g of the TPO-Lphoto-initiator and heat with the hot air gun until the mixture iscompletely blended. Before the mixture hardens, pour it into the heatedMVEMA solution and promptly turn on the rotorstator to beginemulsifying. Gradually increase the rotorstator speed for a few minutes.Slowly drop 2 g of a 5% NaOH solution into the micro-encapsulation. Runthe reaction for 5 minutes and add the melamine formaldehyde 1 mL at atime. Following the formaldehyde, drop 4 g of 5% Acetic Acid solutionand lower the rotostator speed to one. Allow the encapsulation toemulsify for 5 minutes before slowly turning off the rotorstator andtaking the spice jar out of the hot oil bath.

The micro-encapsulation is cooled slowly (30 minutes), either left inthe oil bath until completely cool or wrapped with aluminum foil toslower the decreasing rate of temperature. Once completely cool, themicro-encapsulation can be tested as a slurry for effectiveness andoptimization through a light test; establish a control for this test bycovering up part of the test strip for later observation. Also, recordthe date and time of the light test, along with the amount of time ittakes to evanesce, to further test in different environments of lightexposure.

R. Scaled Up Evanescent Dye Pseudo Master Batch Production

For industrial scale processing, 24 kg pseudo master batch wet powderwas prepared using 30% by weight aqueous evanescent slurry (preparedabove at 50% by weight micro-encapsulated pigment, Segan Industries,Inc. CA), 10% by weight aqueous liquid surfactant (Michelman Corp.ME09730-FD), and 30% by weight powered/pulverized polyethylene (ICOPolymers, LLP 8555.25) and 30% by weight additional polyethylene (BAPOL,LLDPE 2272G). One example sequence of addition includes pre-coating thepowdered polyethylene carrier resin by continuously mixing it in anagitation mixer, adding the liquid emulsion and then continuing to mixuntil the polyethylene powder is uniformly wetted by the emulsion (10minutes). The evanescent slurry is then added consistently to the mixingcomposition and the mixing is continued until the composition isthoroughly mixed and homogenized (10 minutes).

Once mixing is complete, the wet evanescent pseudo master batch is thendried to a uniform granular flowing powder. Upon drying, the driedpseudo master batch can be further compounded prior to utilization orprocessing by the addition of lubricants such as ethylenebis(stearamide) and color stabilizers described in this case such asethyl vinyl acetate. Typically ethylene bis(stearamide) (EBS), is addedat 3-4% of the powdered pseudo master batch.

Each component was added to a mixing vessel and mixed thoroughly to auniform paste. The paste was dried in laminar forces air drier system at120° F. for 2 hours and collected as a large granulated composition (0.1inch diameter average particle size). Dried pseudo master batch could beused directly for PE or PP extrusion or injection molding applicationsbetween 2% to 10% by weight in the molding resin. Alternatively, theresulting pseudo master batch could be palletized using an extrusionpalletizing unit with zone temperatures of 80° C. for 6 temperaturezones, 85° C. for zone 7, a materials handling zone at 120° C., and adie extrusion zone at 120° C. Pellets were cleaved, cooled, and driedusing a front face water ring pelletinzing system. Final pellets couldbe used in injection molding and extrusion from between 3% to 10% byweight.

S. Fluorescent Pink Pseudo Master Batch:

For industrial scale processing, 24 kg pseudo master batch wet powderwas prepared using 20% by weight aqueous pink fluorescent slurry (AuroraPink, SPL-12J pigment, Dayglo Corp.), 10% by weight aqueous liquidsurfactant (Michelman Corp. ME09730-FD), and 35% by weightpowered/pulverized polyethylene (ICO Polymers, LLP 8555.25) and 35% byweight additional polyethylene (BAPOL, LLDPE 2272G). One examplesequence of addition includes pre-coating the powdered polyethylenecarrier resin by continuously mixing it in an agitation mixer, addingthe liquid emulsion and then continuing to mix until the polyethylenepowder is uniformly wetted by the emulsion (10 minutes). The fluorescentslurry is then added consistently to the mixing composition and themixing is continued until the composition is thoroughly mixed andhomogenized (10 minutes).

Once mixing is complete, the wet fluorescent pseudo master batch is thendried to a uniform granular flowing powder. Upon drying, the driedpseudo master batch can be further compounded prior to utilization orprocessing by the addition of lubricants such as ethylenebis(stearamide) and color stabilizers described in this case such asethyl vinyl acetate. Typically ethylene bis(stearamide) (EBS), is addedat 3-4% of the powdered pseudo master batch used and ethyl vinyl acetateis added at 15% of the powdered pseudo master batch used.

Each component was added to a mixing vessel and mixed thoroughly to auniform paste. The paste was dried in laminar forces air drier system at120° F. for 2 hours and collected as a large granulated composition (0.1inch diameter average particle size). Dried pseudo master batch could beused directly for PE or PP extrusion or injection molding applicationsbetween 2% to 10% by weight in the molding resin. Alternatively, theresulting pseudo master batch could be palletized using an extrusionpalletizing unit with zone temperatures of 80° C. for 6 temperaturezones, 85° C. for zone 7, a materials handling zone at 120° C., and adie extrusion zone at 120° C. Pellets were cleaved, cooled, and driedusing a front face water ring pelletinzing system. Final pellets couldbe used in injection molding and extrusion from between 3% to 10% byweight.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is readily apparent to those of ordinary skill in theart in light of the teachings of this invention that certain changes andmodifications may be made thereto without departing from the spirit orscope of the appended claims.

Accordingly, the preceding merely illustrates the principles of theinvention. It will be appreciated that those skilled in the art will beable to devise various arrangements which, although not explicitlydescribed or shown herein, embody the principles of the invention andare included within its spirit and scope. Furthermore, all examples andconditional language recited herein are principally intended to aid thereader in understanding the principles of the invention and the conceptscontributed by the inventors to furthering the art, and are to beconstrued as being without limitation to such specifically recitedexamples and conditions. Moreover, all statements herein recitingprinciples, aspects, and embodiments of the invention as well asspecific examples thereof, are intended to encompass both structural andfunctional equivalents thereof. Additionally, it is intended that suchequivalents include both currently known equivalents and equivalentsdeveloped in the future, i.e., any elements developed that perform thesame function, regardless of structure. The scope of the presentinvention, therefore, is not intended to be limited to the exemplaryembodiments shown and described herein. Rather, the scope and spirit ofpresent invention is embodied by the appended claims.

What is claimed is:
 1. A color change composition comprising: acomposition comprising a color former and a color developer thattransitions from a first color state to a second color state uponapplication of an applied stimulus; and an amount of a copolymersufficient to eliminate background color of the composition duringtransition from a first color state to a second color state.
 2. Thecolor change composition according to claim 1, wherein the copolymercomprises the formula:

where n is an integer from 10 to 1000, m is an integer from 10 to 1000and R is an alkyl, substituted alkyl, alkenyl, substituted alkenyl,alkynyl, substituted alkynyl, acyl, substituted acyl, acyloxy,substituted acyloxy, alkoxycarbonyl, substituted alkoxycarbonyl,carboxyl or substituted carboxyl.
 3. The color change compositionaccording to claim 2, wherein the copolymer comprises the formula:

wherein: n is an integer from 10 to 1000; m is an integer from 10 to1000; and R_(a) is hydrogen, alkyl or substituted alkyl.
 4. The colorchange composition according to claim 3, wherein R_(a) is a C1-C12alkyl.
 5. The color change composition according to claim 3, whereinR_(a) is methyl.
 6. The color change composition according to claim 3,wherein R_(a) is ethyl.
 7. The color change composition according toclaim 3, wherein the ratio of n to m ranges between 1:1 and 1:10.
 8. Thecolor change composition according to claim 7, wherein the ratio of n tom is 1:5.
 9. The color change composition according to claim 3, whereinthe ratio of n to m ranges between 1:1 and 10:1.
 10. The color changecomposition according to claim 9, wherein the ratio of n to m is 5:1.11. The color change composition according to claim 3, wherein thecopolymer is ethyl vinyl acetate.
 12. The color change compositionaccording to claim 11, wherein the ethyl vinyl acetate copolymer has amolecular weight of 5 kDa to 100 kDa.
 13. The color change compositionaccording to claim 11, wherein the ethyl vinyl acetate copolymer has avinyl acetate content which ranges from 5% to 45% by weight.
 14. Thecolor change composition according to claim 2, wherein the copolymercomprises the formula:

wherein: n is an integer from 10 to 1000; m is an integer from 10 to1000; and R_(b) is hydrogen, alkyl or substituted alkyl.
 15. The colorchange composition according to claim 14, wherein R_(b) is a C1-C12alkyl.
 16. The color change composition according to claim 15, whereinR_(b) is a C1-C6 alkyl.
 17. The color change composition according toclaim 15, wherein R_(b) is methyl.
 18. The color change compositionaccording to claim 15, wherein R_(b) is ethyl.
 19. The color changecomposition according to claim 15, wherein R_(b) is butyl.
 20. The colorchange composition according to claim 14, wherein the ratio of n to mranges between 1:1 and 1:10.
 21. The color change composition accordingto claim 14, wherein the ratio of n to m is 1:5.
 22. The color changecomposition according to claim 14, wherein the ratio of n to m rangesbetween 1:1 and 10:1.
 23. The color change composition according toclaim 14, wherein the ratio of n to m is 5:1.
 24. The color changecomposition according to claim 14, wherein the copolymer is ethyleneethyl acrylate.
 25. The color change composition according to claim 14,wherein the copolymer is ethylene butyl acrylate.
 26. The color changecomposition according to claim 14, wherein the copolymer is ethylenemethyl acrylate.
 27. The color change composition according to claim 14,wherein the copolymer has a molecular weight of 5 kDa to 100 kDa. 28.The color change composition according to claim 14, wherein thecopolymer has an acrylate content which ranges from 5% to 45% by weight.29. The color change composition according to claim 1, wherein copolymeris present in the color change composition in an amount of 1% to 10%w/w.
 30. The color change composition according to claim 1, wherein thecolor former changes color in response to a phase transition of thecolor developer.
 31. The color change composition according to claim 30,wherein the phase transition is from solid to liquid.
 32. The colorchange composition according to claim 1, wherein the applied stimulus isa change in temperature.
 33. The color change composition according toclaim 32, wherein the composition transitions from a colorless state toa colored state upon exposure to a change in temperature.
 34. The colorchange composition according to claim 33, wherein the compositiontransitions from a colored state to a colorless state upon exposure to achange in temperature.
 35. The color change composition according toclaim 1, wherein the applied stimulus is solvation.
 36. The color changecomposition according to claim 35, wherein the composition transitionsfrom a colorless state to a colored state upon exposure to increasingsolvation.
 37. The color change composition according to claim 1,wherein the transition is reversible.
 38. The color change compositionaccording to claim 1, wherein the transition is irreversible.
 39. Thecolor change composition according to claim 1, wherein the color formeris a thermochromic dye.
 40. The color change composition according toclaim 39, wherein the thermochromic dye is a leuco dye.
 41. The colorchange composition according to claim 1, wherein the color developer isa glycerol monostearate derivative.
 42. The color change compositionaccording to claim 1, wherein the color former comprises two or moredistinct leuco dyes.
 43. The color change composition according to claim42, wherein the two or more distinct leuco dyes exhibit opposingtransition characteristics in response to the same applied stimulus. 44.The color change composition according to claim 43, wherein the colorchange composition transitions from a red color state to a green colorstate upon application of the applied stimulus.
 45. The color changecomposition according to claim 1, wherein the color developer consistsof a glycerol monostearate derivative.
 46. A method of making a colorchange composition, the method comprising: combining a compositioncomprising a color former and a color developer with an amount of acopolymer to produce a color change composition which changes from afirst color state to a second color state upon application of an appliedstimulus.
 47. The method according to claim 46, wherein the color formerand color developer composition is combined with the copolymer as acolor former-color developer pseudo master batch composition.
 48. Themethod according to claim 47, wherein the pseudo master batch isproduced by combining an aqueous slurry of the color former and colordeveloper with a plastic emulsifier and a plastic resin to produce amixture and flash drying the mixture to produce a color former-colordeveloper pseudo master batch composition.
 49. The method according toclaim 48, wherein the emulsifier is an anionic emulsifier.
 50. Themethod according to claim 48, wherein the emulsifier is a cationicemulsifier.
 51. The method according to claim 48, wherein the emulsifieris a non-ionic emulsifier.
 52. The method according to claim 48, whereinthe pseudo master batch color former-color developer composition is ingranular form.
 53. The method according to claim 48, wherein the pseudomaster batch color former-color developer composition is a powder. 54.The method according to claim 48, wherein the pseudo master batch colorformer-color developer composition is in the form of flakes.
 55. Themethod according to claim 46, wherein the copolymer comprises theformula:

where n is an integer from 10 to 1000, m is an integer from 10 to 1000and R is an alkyl, substituted alkyl, alkenyl, substituted alkenyl,alkynyl, substituted alkynyl, acyl, substituted acyl, acyloxy,substituted acyloxy, alkoxycarbonyl, substituted alkoxycarbonyl,carboxyl or substituted carboxyl.
 56. The method according to claim 55,wherein the copolymer comprises the formula:

wherein: n is an integer from 10 to 1000; m is an integer from 10 to1000; and R_(a) is hydrogen, alkyl or substituted alkyl.
 57. The methodaccording to claim 56, wherein R_(a) is a C1-C12 alkyl.
 58. The methodaccording to claim 56, wherein R_(a) is methyl.
 59. The method accordingto claim 56, wherein the ratio of n to m ranges between 1:1 and 1:10.60. The method according to claim 56, wherein the ratio of n to m rangesbetween 1:1 and 10:1.
 61. The method according to claim 56, wherein thecopolymer is ethyl vinyl acetate.
 62. The method according to claim 61,wherein the ethyl vinyl acetate copolymer has a vinyl acetate contentwhich ranges from 5% to 45% by weight.
 63. The method according to claim55, wherein the copolymer comprises the formula:

wherein: n is an integer from 10 to 1000; m is an integer from 10 to1000; and R_(b) is hydrogen, alkyl or substituted alkyl.
 64. The methodaccording to claim 63, wherein R_(b) is a C1-C12 alkyl.
 65. The methodaccording to claim 63, wherein R_(b) is a C1-C6 alkyl.
 66. The methodaccording to claim 63, wherein R_(b) is methyl.
 67. The method accordingto claim 63, wherein R_(b) is ethyl.
 68. The method according to claim63, wherein R_(b) is butyl.
 69. The method according to claim 63,wherein the ratio of n to m ranges between 1:1 and 1:10.
 70. The methodaccording to claim 63, wherein the ratio of n to m ranges between 1:1and 10:1.
 71. The method according to claim 63, wherein the copolymer isethylene ethyl acrylate.
 72. The method according to claim 63, whereinthe copolymer is ethylene butyl acrylate.
 73. The method according toclaim 63, wherein the copolymer is ethylene methyl acrylate.
 74. Themethod according to claim 46, wherein copolymer is combined with thecolor former and color developer composition in an amount of 1% to 10%w/w.
 75. The method according to claim 46, wherein the color formerchanges color in response to a phase transition of the color developer.76. The method according to claim 46, wherein the phase transition isfrom solid to liquid.
 77. The method according to claim 46, wherein theapplied stimulus is a change in temperature.
 78. The method according toclaim 46, wherein the transition is reversible.
 79. The method accordingto claim 46, wherein the transition is irreversible.
 80. The methodaccording to claim 46, wherein the color former is a thermochromic dye.81. The method according to claim 80, wherein the thermochromic dye is aleuco dye.
 82. The method according to claim 46, wherein the colordeveloper is a glycerol monostearate derivative.
 83. The methodaccording to claim 46, wherein the color former comprises two or moredistinct leuco dyes.
 84. The method according to claim 83, wherein thethe two or more distinct leuco dyes exhibit opposing transitioncharacteristics in response to the same applied stimulus.
 85. The methodaccording to claim 46, wherein the color developer consists of aglycerol monostearate derivative.
 86. A method of making a pseudo masterbatch composition, the method comprising: contacting an aqueouscomposition and a powdered plastic resin with a plasticizing emulsifierto produce a plasticized composition; and flash drying the plasticizedmixture to produce a pseudo master batch composition.
 87. The methodaccording to claim 86, wherein the aqueous composition is a slurry. 88.The method according to claim 87, wherein the slurry comprises acompound that is microencapsulated.
 89. The method according to claim86, wherein the aqueous composition comprises a compound from the groupconsisting of dyes, thermochromic agents, photochromic agents andpigments.
 90. The method according to claim 89, wherein the aqueouscomposition comprises a leuco dye.
 91. The method according to claim 89,wherein the aqueous composition comprises a microencapsulated leuco dye.92. The method according to claim 86, wherein flash drying comprisesspray drying.
 93. The method according to claim 86, wherein flash dryingproduces a granular pseudo master batch composition.
 94. A homogenousgranulated or powdered pseudo master batch composition comprising: oneor more non-plastic compounds; a plastic resin; and a plasticizingemulsifier.
 95. A homogeneous granulated or powdered pseudo master batchcomposition comprising: a first plastic composition; a plastic resin;and a plasticizing emulsifier.
 96. A method of making a leuco-dye pseudomaster batch composition, comprising: contacting an aqueous leuco dyecomposition and a powdered plastic resin with a plasticizing emulsifierto produce a plasticized leuco dye composition; and flash drying theplasticized leuco dye composition to produce a leuco dye pseudo masterbatch composition.
 97. The method according to claim 96, wherein theleuco dye is microencapsulated.
 98. The method according to claim 96,wherein the aqueous leuco dye composition is a slurry.
 99. A homogeneouspowdered leuco dye-plastic resin pseudo master batch composition,comprising: a leuco dye; a plastic resin; and a plasticizing emulsifier.100. A method of making a emulsified slurry composition, the methodcomprising: contacting an aqueous slurry comprising one or moremicroencapsulated compounds with a powdered hydrophobic composition anda plasticizing emulsifier to produce plasticized composition; and dryingthe plasticized composition to produce a plasticized slurry compositioncomprising one or more microencapsulated compounds.
 101. The methodaccording to claim 100, wherein the microencapsulated compound comprisesa color change compound.
 102. The method according to claim 101, whereinthe color change compound is a leuco dye.
 103. A method of making apseudo master batch composition, the method comprising: contacting ahydrophilic composition and a hydrophobic composition with aplasticizing emulsifier to produce a plasticized hydrophilic-hydrophobiccomposition; and flash drying the plasticized hydrophilic-hydrophobiccomposition to produce a pseudo master batch composition.
 104. Themethod according to claim 103, wherein the hydrophilic composition is anaqueous slurry.
 105. The method according to claim 103, wherein thehydrophilic composition comprises wood.
 106. The method according toclaim 105, wherein the hydrophilic composition comprises a slurry ofwood powder.
 107. The method according to claim 105, wherein thehydrophobic composition comprises polypropylene.
 108. A method of makinga wood-plastic pseudo master batch composition, the method comprising:combining a wood composition and a powdered plastic resin with aplasticizing emulsifier to produce a plasticized wood-plastic resincomposition; and flash drying the plasticized wood-plastic resincomposition to produce a wood-plastic pseudo master batch composition.109. The method according to claim 108, wherein the wood composition isa slurry of wood powder.
 110. The method according to claim 108, whereinthe wood composition is a wood powder.
 111. A homogeneous powderedwood-plastic pseudo master batch composition, comprising: wood; plasticresin; and a plasticizing emulsifier.
 112. A method of making a pseudomaster batch composition, the method comprising: contacting acomposition comprising one or more granulated recycled materials and apowdered plastic resin with a plasticizing emulsifier to produce aplasticized composition; flash drying the plasticized composition toproduce a pseudo master batch composition comprising one or morerecycled materials.
 113. The method according to claim 112, wherein therecycled materials is selected from the group consisting of recycledwood, recycled plastic, recycled paper, recycled glass, recycledasphalt, recycled concrete and recycled cement.
 114. A homogeneouspowdered recycled material-plastic pseudo master batch composition,comprising: one or more recycled materials; plastic resin; and aplasticizing emulsifier.
 115. The composition according to claim 114,wherein the recycled materials is selected from the group consisting ofrecycled wood, recycled plastic, recycled paper, recycled glass,recycled asphalt, recycled concrete and recycled cement.
 116. A methodof converting a dry hydrophobic compound into a composition capable ofbeing homogenized with an aqueous hydrophilic composition, the methodcomprising: contacting a hydrophobic composition with a plasticizingemulsifier to produce a plasticized hydrophobic composition.
 117. Amethod of converting an aqueous hydrophilic compound into a compositioncapable of being homogenized with a dry hydrophobic composition, themethod comprising: contacting a hydrophilic composition with aplasticizing emulsifier to produce a plasticized hydrophiliccomposition.